TWI564339B - A polymerizable compound, a liquid crystal alignment device, a liquid crystal alignment film, and a liquid crystal display device, and a method of manufacturing the liquid crystal display device - Google Patents

Description

Polymerizable compound, liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display element, and manufacturing method of liquid crystal display element

The present invention relates to a polymerizable compound, a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element which can be used in the vertical alignment mode liquid crystal display device which is produced by irradiating ultraviolet rays in a state in which a liquid crystal molecule is applied with a voltage. A method of manufacturing a liquid crystal display element.

The liquid crystal display element generally has an electrode and a liquid crystal which form a liquid crystal alignment film that aligns the liquid crystal. As a material of the liquid crystal alignment agent for forming the liquid crystal alignment film, an organic liquid crystal alignment film material such as polyimine or a polyoxyalkylene liquid crystal alignment film material obtained by polycondensing an alkoxysilane or the like is known. (Refer to Patent Document 1 and Patent Document 2). As a display mode of the liquid crystal display element, there is a method in which liquid crystal molecules perpendicular to the substrate alignment are responded by an electric field (also referred to as a vertical alignment (VA) method), and the liquid crystal display element includes, for the manufacturing process, The step of irradiating ultraviolet rays while applying a voltage to the liquid crystal molecules.

In the liquid crystal display device of such a vertical alignment type, a photopolymerizable compound is added to the liquid crystal composition in advance, and is used together with a vertical alignment film such as polyimide, and the ultraviolet ray is applied to the liquid crystal cell while being irradiated with ultraviolet rays. A technique for responding to a liquid crystal (see, for example, Patent Document 3, Patent Document 4, and Non-Patent Document 1) (PSA (Polymer sustained Alignment) type liquid crystal display). The tilt direction of the liquid crystal molecules generally responsive to the electric field can be controlled by a protrusion provided on the substrate or a slit provided in the display electrode, but a photopolymerizable compound is added to the liquid crystal composition and a voltage is applied to the liquid crystal cell. When the ultraviolet ray is irradiated, the liquid crystal molecules are formed on the liquid crystal alignment film by the memory structure in which the liquid crystal molecules are tilted. Therefore, the response speed of the liquid crystal display element is higher than that of the method of controlling the tilt direction of the liquid crystal molecules only by protrusions or slits. For the quick.

In addition, it has been reported that even if a photopolymerizable compound is added to a liquid crystal alignment film without being added to a liquid crystal alignment film, the response speed of the liquid crystal display element can be accelerated (SC-PVA liquid crystal display) (for example, refer to the non-patent) Literature 2).

[Advanced technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 09-281502

[Patent Document 2] JP-A-2005-250244

[Patent Document 3] JP-A-2003-307720

[Patent Document 4] JP-A-2004-302061

[Non-patent literature]

[Non-Patent Document 1] K. Hanaoka, SID 04 DIGEST, P.1200-1202

[Non-Patent Document 2] K.H Y.-J.Lee, SID 09 DIGEST, P.666-668

However, it is expected to further accelerate the response speed of the liquid crystal display element. In addition, it is considered that the reaction rate of the liquid crystal display element can be increased by increasing the amount of the photopolymerizable compound to be added. However, when the photopolymerizable compound is left unreacted in the liquid crystal and directly remains, it becomes an impurity (contamination) and becomes a liquid crystal. Since the reliability of the element is displayed, a polymerizable compound capable of accelerating the response speed with a small addition amount is expected.

An object of the present invention is to solve the problems of the prior art, and to provide a polymerizable compound, a liquid crystal alignment agent, a liquid crystal alignment film, a liquid crystal display element, and a liquid crystal display element which can improve the response speed of a liquid crystal display element of a vertical alignment type. method.

The polymerizable compound of the present invention which solves the above problems is characterized by the following formula (1).

(In the formula (1), V represents a single bond or -R ¹ O-, R ¹ is a linear or branched alkyl group having 1 to 10 carbon atoms, and W represents a single bond or -OR ² -, and R ² is straight a chain or branch having a carbon number of 1 to 10 alkyl groups).

Further, the liquid crystal alignment agent of the present invention is characterized in that it has a polymerizable compound, a polymer which forms a liquid crystal alignment film in which a liquid crystal is aligned, and a solvent.

The polymer system forming the liquid crystal alignment film in which the liquid crystal is aligned perpendicularly may further comprise a polyimine precursor selected from the group consisting of a side chain having a liquid crystal alignment direction, and the ruthenium imidization of the polyimine precursor At least one of the obtained polyimine.

Further, the polymer forming the liquid crystal alignment film in which the liquid crystal is aligned perpendicularly may contain a polyoxyalkylene having a side chain in which the liquid crystal is aligned perpendicularly.

Further, the polyoxyalkylene is preferably a photoreactive side chain.

Further, the polyoxyalkylene is preferably obtained by subjecting at least one selected from the group consisting of alkoxydecane and a condensate thereof to polycondensation.

The alkoxydecane may contain an alkoxydecane represented by the following formula (7).

R ¹¹ Si(OR ¹² ) ₃ (7)

(R ¹¹ represents a hydrocarbon group having 8 to 30 carbon atoms which may be substituted by hydrogen with a fluorine atom, and R ¹² represents an alkyl group having 1 to 5 carbon atoms).

Further, the alkoxydecane may further contain the following formula (8).

R ¹³ Si(OR ¹⁴ ) ₃ (8)

(R ¹³ represents an alkyl group substituted with at least one hydrogen selected from the group consisting of a propenyl group, a methacryl group, a vinyl group, an epoxy group, a vinyloxy group, and a propyleneoxy group, and R ¹⁴ represents an alkyl group having 1 to 5 carbon atoms)

The liquid crystal alignment film of the present invention is characterized in that the liquid crystal alignment agent is applied onto a substrate and fired.

Further, the liquid crystal display device of the present invention is characterized in that it has a liquid crystal cell which is produced by irradiating ultraviolet rays by applying a voltage to the liquid crystal or the liquid crystal alignment film.

Moreover, the method for producing a liquid crystal display device of the present invention is characterized in that the polymerizable compound is contained in a liquid crystal or a liquid crystal alignment film, and a liquid crystal cell is produced by applying a voltage while applying a voltage.

The present invention provides a novel polymerizable compound which can improve the response speed of a liquid crystal display element of a vertical alignment mode. By using the polymerizable compound, it is possible to accelerate the vertical alignment type liquid crystal display element of the response speed. Further, in the liquid crystal alignment agent, even when the amount of the polymerizable compound added is small or the amount of irradiation of ultraviolet rays is small, the response speed can be sufficiently increased.

[Type of implementation of the invention]

The invention will be described in detail below.

The polymerizable compound of the present invention is represented by the above formula (1). With respect to the above formula (1), V represents a single bond or -R ¹ O-, and R ¹ is a linear or branched alkyl group having 1 to 10 carbon atoms, preferably -R ¹ O-, and R ¹ is straight. A chain or branch having 2 to 6 carbon atoms. Further, W represents a single bond or -OR ² -, and R ² is a linear or branched alkyl group having 1 to 10 carbon atoms, preferably -OR ² -, and R ² is a linear or branched carbon number 2 ~6 alkylene. Moreover, V and W may have the same or different structures, but are easier to synthesize in the same structure.

The polymerizable compound represented by the above formula (1) may be a compound having a specific structure of an α-methyl-γ-butyrolactone group having a polymerizable group at both terminals, so that the polymer has a rigid structure and has The excellent liquid crystal alignment fixing ability can be greatly improved in response speed by using a vertical alignment type liquid crystal display element such as a PSA type liquid crystal display or an SC-PVA type liquid crystal display as shown in the later-described embodiment. In the present invention, the polymerizable group at both ends must be an α-methyl-γ-butyrolactone group. For example, Patent Document 1 has an acrylate group, a methacrylate group, a vinyl group, and an ethylene group. A compound having a polymerizable group such as an oxy group or an epoxy group cannot greatly increase the response speed of the liquid crystal display device of the vertical alignment type as a small amount of the compound represented by the above formula (1) of the present invention. Further, in general, during the formation of the liquid crystal alignment film, the solvent is completely removed, and the firing step at a high temperature is included, but a polymerizable group such as an acrylate group, a methacrylate group, a vinyl group, a vinyloxy group, or an epoxy group is contained. The compound lacks thermal stability and is difficult to withstand firing at high temperatures. On the other hand, the polymerizable compound represented by the above formula (1) of the present invention has a structure which lacks thermal polymerization property, and thus can be sufficiently resistant to high temperatures, for example, at a firing temperature of 200 ° C or higher.

The polymerizable compound of the present invention represented by the above formula (1) can be synthesized by a combination of methods in organic synthetic chemistry, and the synthesis method is not particularly limited. For example, 2-(bromomethyl) can be used with SnCl ₂ by the method proposed by Talaga et al., P. Talaga, M. Schaeffer, C. Benezra and JL Stampf, Synthesis, 530 (1990), as shown in the following reaction formula. Acrylic acid (2-(bromomethyl) propenoic acid) is synthesized by reaction with an aldehyde or a ketone. Further, Amberlyst 15 is a strongly acidic ion exchange resin manufactured by Rohm and Haas Company.

(wherein R' represents a monovalent organic group).

Further, 2-(bromomethyl)acrylic acid can be represented by the following reaction formula by Ramarajan et al., K. Ramarajan, K. Kamalingam, DJ O'Donnell and KD Berlin, Organic Synthesis, vol. 61, 56-59 (1983). The method of the proposal is synthesized.

Specific examples of the synthesis are as follows: when the polymerizable compound represented by the above formula (1) wherein R is -R ¹ O- and W is -OR ² - and R ¹ and R ² are the same, the following reaction formula is shown. 2 methods.

Further, when the polymerizable compound represented by the above formula (1) is synthesized in which R ¹ and R ² are different, a method represented by the following reaction formula may be mentioned.

When the polymerizable compound represented by the above formula (1) in which V and W are a single bond is synthesized, the method represented by the following reaction formula can be mentioned.

The polymerizable compound represented by the above formula (1) may be contained in a liquid crystal alignment agent. Specifically, the liquid crystal alignment agent of the present invention has a polymerizable compound represented by the above formula (1), a polymer which forms a liquid crystal alignment film in which a liquid crystal is aligned, and a solvent. For example, a polymerizable compound represented by the above formula (1) is added to a known liquid crystal alignment agent for vertical alignment. Further, the liquid crystal alignment agent is a solution for producing a liquid crystal alignment film, and the liquid crystal alignment film is a film having a liquid crystal alignment direction, and is a film having a perpendicular direction in the present invention.

A polymer which forms a liquid crystal alignment film in which the liquid crystal is aligned vertically is not particularly limited as long as the liquid crystal on the liquid crystal alignment film formed on the substrate is aligned in the vertical direction, even if it is a polyimide precursor. Or an organic liquid crystal alignment film material such as polyimine obtained by ruthenium imidization of the polyimine precursor, or a polyester, a (meth) acrylonitrile-based or a polyoxyalkylene-based liquid crystal alignment film. The material is preferably, for example, a polymer having a side chain in which the liquid crystal is aligned vertically, and for example, a polyimine precursor selected from a side chain having a liquid crystal alignment direction, and the polyimine precursor is selected. At least one of a polyimine obtained by ruthenium imidization and a polyoxyalkylene having a side chain in which a liquid crystal is aligned is vertical. The polymer which forms the liquid crystal alignment film in which the liquid crystal is aligned perpendicularly may be only one type or two or more types. Further, examples of the polyimine precursor include polyamic acid or polyphthalamide.

The side chain in which the liquid crystal is aligned in the vertical direction is not particularly limited as long as it can align the liquid crystal to the substrate in the vertical direction, and examples thereof include a long-chain alkyl group and a long-chain alkyl group having a ring structure or a branched structure. A hydrocarbon group such as a steroid group or a group in which one or all of hydrogen of these groups is partially substituted by a fluorine atom or the like. Of course, there may be two or more types of side chains in which the liquid crystals are aligned vertically. The vertical side chain of the liquid crystal alignment can be directly bonded to the main chain of the polymer such as polyimine precursor, polythenimine or polyoxyalkylene, and can be directly bonded to the polyamine structure and the polyimine. The skeleton or the polyoxyalkylene skeleton or the like may also be bonded via a suitable bonding group. Examples of the side chain in which the liquid crystal is aligned perpendicularly include a hydrocarbon group having a carbon number of 8 to 30, preferably 8 to 22, which may be substituted by fluorine, and specific examples thereof include an alkyl group, a fluoroalkyl group, an alkenyl group and a benzene group. Ethyl, styrenealkyl, naphthyl, fluorophenylalkyl, and the like. Other examples of the side chain in which the liquid crystal is aligned perpendicularly are exemplified by the following formula (a).

(In the formula (a), l, m and n each independently represent an integer of 0 or 1, and R ³ represents an alkylene group having 2 to 6 carbon atoms, -O-, -COO-, -OCO-, -NHCO-, - CONH- or an alkylene-ether group having 1 to 3 carbon atoms, R ⁴ , R ⁵ and R ⁶ each independently represent a phenyl or cycloalkyl group, and R ⁷ represents hydrogen, an alkyl group having 2 to 24 carbon atoms or A fluorine-containing alkyl group, a monovalent aromatic ring, a monovalent aliphatic ring, a monovalent heterocyclic ring or a monovalent large cyclic substituent thereof.

Further, from the viewpoint of easiness of synthesis, R ³ in the above formula (a) is preferably an alkyl-ether group having -O-, -COO-, -CONH- or a carbon number of 1-3.

Further, R ⁴ , R ⁵ and R ⁶ in the formula (a) are represented by the following Table 1, from the viewpoints of easiness of synthesis and ability to align the liquid crystal to be vertical, as shown in the following Table 1, l, m, n, R ⁴ , R ⁵ The combination of R ⁶ is preferred.

When at least one of l, m and n is 1, R ⁷ in the formula (a) is preferably hydrogen or an alkyl group having 2 to 14 carbon atoms or an alkyl group containing fluorine, more preferably hydrogen or carbon number 2~ An alkyl group of 12 or an alkyl group containing fluorine. Further, when l, m and n are all 0, R ^{7 is} preferably an alkyl group having 12 to 22 carbon atoms or an alkyl group containing fluorine, a monovalent aromatic ring, a monovalent aliphatic ring, a monovalent heterocyclic ring, and the like. It is preferably a one-valent large cyclic substituent, more preferably an alkyl group having 12 to 20 carbon atoms or an alkyl group containing fluorine.

The amount of the side chain in which the liquid crystal is aligned vertically is not particularly limited as long as the liquid crystal alignment film can align the liquid crystal in a vertical range. However, in the liquid crystal display element including the liquid crystal alignment film, the amount of the side chain in which the liquid crystal alignment is perpendicular is preferably as small as possible within a range that does not impair the display characteristics of the voltage such as the voltage holding ratio or the accumulation of the residual DC voltage. .

Moreover, the polymer having the side chain of the liquid crystal alignment in the vertical direction has the ability to align the liquid crystal in a vertical direction, and is different according to the structure in which the liquid crystal is aligned in a vertical side chain, but generally, the liquid crystal is aligned in a vertical side chain. When the amount of the liquid crystal is increased, the ability to vertically align the liquid crystal is increased, and when it is reduced, it is lowered. Moreover, when it has a cyclic structure, compared with the one which does not have a cyclic structure, it exists in the tendency which improves the liquid-crystal alignment orthogonal.

Further, it is preferred to form a polymer having a liquid crystal alignment film in which the liquid crystal is aligned in a vertical direction to have a photoreactive side chain. Response speed if there is a photoreactive side chain The degree can be further improved. The photoreactive side chain is a side chain having a functional group (hereinafter also referred to as a photoreactive group) capable of forming a covalent bond by irradiation with light such as ultraviolet rays (UV), and the structure can be obtained by having such a capability. Not limited. Examples of the photoreactive side chain include a vinyl group, a propylene group, a methacryl group, an allyl group, a styryl group, a cinnamyl group, a chalcone group, a coumarin group, and a malayan group. Examples of the side chain of a guanamine, an epoxy group, a vinyloxy group, and a propyleneoxy group include these photoreactive basic bodies, or an alkyl group in which hydrogen is replaced by these photoreactive groups. The hydrogen to be substituted may be one or more, preferably one. The number of alkyl carbon atoms in which hydrogen is replaced by a photoreactive group is preferably from 1 to 30, more preferably from 1 to 10, still more preferably from 1 to 5, from the viewpoints of response speed and vertical alignment. Of course, it is also possible to have two or more kinds of photoreactive side chains. The photoreactive side chain may be directly bonded to the main chain of a polymer such as a polyimine precursor, a polyimine or a polyoxyalkylene, or may be bonded via a suitable bonding group. Examples of the photoreactive side chain include those represented by the following formula (b).

[Chemical 9]-R ⁸ -R ⁹ -R ¹⁰ (b)

(In the formula (b), R ⁸ represents a single bond or -CH ₂ -, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N Any one of (CH ₃ )-, -CON(CH ₃ )-, -N(CH ₃ )CO-, and R ⁹ represents a single bond or an alkyl group having 1 to 20 carbon atoms which may be substituted by a fluorine atom or substituted by a fluorine atom. The alkyl-CH ₂ - may be optionally substituted by -CF ₂ - or -CH=CH-, and may be substituted for any of the following groups when they are not adjacent to each other; -O-, -COO- , -OCO-, -NHCO-, -CONH-, -NH-, a divalent carbocyclic ring, a divalent heterocyclic ring. R ¹⁰ represents a vinyl group, a propenyl group, a methacryl group, an allyl group, a styryl group, N(CH ₂ CHCH ₂ ) ₂ or the structure shown by the following formula)

Further, R ⁸ in the above formula (b) can be formed by a general organic synthesis method, but from the viewpoint of easiness of synthesis, -CH ₂ -, -O-, -COO-, -NHCO-, - NH-, -CH ₂ O- is preferred.

Further, the carbocyclic or heterocyclic ring of the divalent carbocyclic ring or the divalent heterocyclic ring of any -CH ₂ - substituted for R ⁹ may specifically be as follows, but is not limited thereto.

R ¹⁰ is preferably a vinyl group, a propylene group, a methacryl group, an allyl group, a styryl group, -N(CH ₂ CHCH ₂ ) ₂ or a structure represented by the following formula from the viewpoint of photoreactivity.

Further, the above formula (b) is preferably the following structure.

When the amount of the photoreactive side chain is reacted by irradiation with ultraviolet rays to form a covalent bond, the range of the response speed of the liquid crystal can be accelerated, and the response speed of the liquid crystal is further accelerated, so as not to affect other characteristics. As much as possible.

Further, a polymer which forms a liquid crystal alignment film which is perpendicular to the liquid crystal may be formed, and may have other side chains in addition to the side chain or the photoreactive side chain in which the liquid crystal is aligned. Examples of the other side chain include a hydrocarbon group having 1 to 6 carbon atoms which may be substituted by hydrogen or a hetero atom, a halogen atom, an amine group, a glycidoxy group, a thiol group, an isocyanate group or a guanidino group. The polyoxyalkylene having these groups can improve the adhesion of the obtained liquid crystal alignment film to the substrate or the affinity with liquid crystal molecules.

The method for producing a polymer which forms such a liquid crystal alignment film which is perpendicular to the liquid crystal alignment film is not particularly limited. For example, when a polyglycine having a side chain in which the liquid crystal is aligned is formed, a diamine and a tetracarboxylic dianhydride are used. In the method of obtaining a poly-proline, the method of copolymerizing a diamine having a side chain which is perpendicular to the liquid crystal or a tetracarboxylic dianhydride having a side chain in which the liquid crystal is aligned is simple. Further, when the polymer forming the liquid crystal alignment film in which the liquid crystal is aligned perpendicularly contains a photoreactive side chain, only the diamine having a photoreactive side chain or the tetracarboxylic dianhydride having a photoreactive side chain is copolymerized. Just fine.

Examples of the diamine having a side chain in which the liquid crystal is aligned in a vertical direction include a long-chain alkyl group, a long-chain alkyl group, a group having a ring structure or a branched structure, a hydrocarbon group such as a steroid group, or a hydrogen group of these groups. A diamine in which a part of the fluorine atom is partially or wholly substituted with a side chain, and examples thereof include a diamine having a side chain represented by the above formula (a). More specifically, for example, a diamine having a hydrocarbon group having 8 to 30 carbon atoms in which hydrogen can be substituted by fluorine or a diamine represented by the following formulas (2), (3), (4), and (5) However, it is not limited to this.

(The definitions of l, m, n, R ³ to R ^{7 in} the formula (2) are the same as those in the above formula (a))

(In the formulae (3) and (4), A ₁₀ represents -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO- or -NH-, A ₁₁ Represents a single bond or a phenyl group, a represents the same structure as the side chain perpendicular to the liquid crystal alignment shown in the above formula (a), and a' represents a side chain perpendicular to the liquid crystal alignment shown in the above formula (a) The same structure takes out a divalent group of the structure of an element such as hydrogen)

(In the formula (5), A ₁₄ is an alkyl group having 3 to 20 carbon atoms which may be substituted by a fluorine atom, A ₁₅ is a 1,4-cyclohexyl group or a 1,4-phenylene group, and A ₁₆ is an oxygen atom or -COO-* (but with the "*" bond combined with A ₁₅ ), A ₁₇ is an oxygen atom or -COO-* (but the bond with "*" is bonded to (CH ₂ )a ₂ ). Further, a ₁ is an integer of 0 or 1, a ₂ is an integer of 2 to 10, and a ₃ is an integer of 0 or 1.

Bonding position of formula (2) in the two group (-NH ₂₎ of and defined. Specifically, the bonding group of the side chain may be a position of 2, 3 on the benzene ring, a position of 2, 4, a position of 2, 5, a position of 2, 6, a position of 3, 4, 3,5 position. Among them, from the viewpoint of reactivity in synthesizing polyamic acid, it is preferred to have a position of 2, 4, a position of 2, 5, or a position of 3, 5. When the ease of synthesizing a diamine is added, it is preferable to use a position of 2, 4 or a position of 3, 5.

Specific examples of the formula (2) include diamines represented by the following formulas [A-1] to [A-24], but are not limited thereto.

(In the formula [A-1] to the formula [A-5], A ₁ is an alkyl group having 2 to 24 carbon atoms or an alkyl group containing fluorine)

(In the formula [A-6] and the formula [A-7], A ₂ represents -O-, -OCH ₂ -, -CH ₂ O-, -COOCH ₂ - or -CH ₂ OCO-, and A ₃ is a carbon number. 1 to 22 alkyl groups, alkoxy groups, fluorine-containing alkyl groups or fluorine-containing alkoxy groups)

(In the formula [A-8] to the formula [A-10], A ₄ represents -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O -, -OCH ₂ - or -CH ₂ -, A ₅ is an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group)

(In the formula [A-11] and the formula [A-12], A ₆ represents -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O -, -OCH ₂ -, -CH ₂ -, -O- or -NH-, A ₇ is a fluoro group, a cyano group, a trifluoromethyl group, a nitro group, an azo group, a methyl group, an ethyl group, a Alkoxy or hydroxy)

(In the formula [A-13] and the formula [A-14], A ₈ is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomer of the 1,4-cyclohexyl group is a trans isomer)

(In the formula [A-15] and the formula [A-16], A ₉ is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomer of the 1,4-cyclohexyl group is a trans isomer)

Specific examples of the diamine represented by the formula (3) include the diamines represented by the following formulas [A-25] to [A-30], but are not limited thereto.

(In the formula [A-25] to the formula [A-30], A ₁₂ represents -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO- or -NH -, A ₁₃ represents an alkyl group having 1 to 22 carbon atoms or an alkyl group containing fluorine)

Specific examples of the diamine represented by the formula (4) include a diamine represented by the following formula [A-31] to the formula [A-32], but are not limited thereto.

Among them, [A-1], [A-2], [A-3], [A-4], [A-5], [from the viewpoint of the ability to align the liquid crystal in a vertical direction and the response speed of the liquid crystal. The diamines of A-25], [A-26], [A-27], [A-28], [A-29], and [A-30] are preferred.

The diamine may be used in one type or in a mixture of two or more types depending on characteristics such as liquid crystal alignment property, tilt angle, voltage holding property, and storage charge when it is used as a liquid crystal alignment film.

The diamine having such a side chain in which the liquid crystal is aligned in a vertical direction is preferably used in an amount of 5 to 50 mol%, preferably 10 to 40 mol%, of the diamine component used for the synthesis of the polyamic acid. The ear % is a diamine having a side chain in which the liquid crystal is aligned vertically, and particularly preferably 15 to 30 mol%. When the diamine having a side chain in which the liquid crystal is aligned vertically is used in an amount of 5 to 50 mol% of the diamine component used in the synthesis of polylysine, the response speed is improved or the liquid crystal alignment is immobilized. The point of view is particularly good.

Examples of the diamine having a photoreactive side chain include a vinyl group, a propylene group, a methacryl group, an allyl group, a styryl group, a cinnamyl group, a chalconyl group, a coumarin group, and a maleimide group. Examples of the diamine having a photoreactive group such as an epoxy group, a vinyloxy group or a propyleneoxy group as a side chain include a diamine having a side chain represented by the above formula (b). More specifically, for example, the diamine represented by the following general formula (6) can be mentioned, but it is not limited thereto.

(The definitions of R ⁸ , R ⁹ and R ¹⁰ in the formula (6) are the same as those in the above formula (b)).

The bonding position of the two amine groups (-NH ₂ ) in the formula (6) is not limited. Specific examples of the bonding group of the side chain include a position of 2, 3 on the benzene ring, a position of 2, 4, a position of 2, 5, a position of 2, 6, a position of 3, 4, and 3, 5 location. Among them, from the viewpoint of reactivity in synthesizing polyamic acid, it is preferred to have a position of 2, 4, a position of 2, 5, or a position of 3, 5. In addition to the ease of synthesizing the diamine, it is preferred to have a position of 2, 4 or a position of 3, 5.

Specific examples of the diamine having a photoreactive side chain include the following compounds, but are not limited thereto.

(wherein X is a single bond or a bonding group selected from -O-, -COO-, -NHCO-, -NH-, and Y is a single bond or an unsubstituted or substituted by a fluorine atom: 1 to 20 carbon atoms Alkyl

The diamine having the photoreactive side chain can be used in a liquid crystal alignment, a tilt angle, a voltage holding property, a charge storage property, and the like, and a response speed of a liquid crystal when used as a liquid crystal display element. Or use 2 or more types.

Further, the diamine having such a photoreactive side chain is preferably used in an amount of 10 to 70 mol%, preferably 20 to 60 mol%, based on the diamine component of the synthesis of polyamic acid. Good for 30~50%.

Further, the polyamine can be used as a diamine other than the diamine having the above-mentioned side chain perpendicular to the liquid crystal alignment or the diamine having a photoreactive side chain, without impairing the effects of the present invention. Use the ingredients together. Specific examples thereof include p-phenylenediamine, 2,3,5,6-tetramethyl-P-phenylenediamine, and 2,5-dimethyl-p-phenylene Amine, m-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,5-diamine Phenolic, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-di Amino resorcinol, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy- 4,4'-Diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl , 3,3'-difluoro-4,4'-biphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3,4'-diamine linkage Phenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenyl Methane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodi Phenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4 '-Diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyldiphenylamine, 3,3 '-sulfonyldiphenylamine, bis(4-aminophenyl)decane, bis(3-aminophenyl)decane, dimethyl-bis(4-aminophenyl)decane, dimethyl-double (3-Aminophenyl)decane, 4,4'-thiodiphenylamine, 3,3'-thiodiphenylamine, 4,4'-diaminodiphenyl Amine, 3,3'-diaminodiphenylamine, 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'-diaminodi Phenylamine, N-methyl(4,4'-diaminodiphenyl)amine, N-methyl(3,3'-diaminodiphenyl)amine, N-methyl (3,4 '-Diaminodiphenyl)amine, N-methyl(2,2'-diaminodiphenyl)amine, N-methyl(2,3'-diaminodiphenyl)amine, 4 , 4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4-diaminonaphthyl, 2, 2'-Diaminobenzophenone, 2,3'-diaminobenzophenone, 1,5-diaminonaphthyl, 1,6-diaminonaphthyl, 1,7-diamine Naphthyl, 1,8-diaminonaphthyl, 2,5-diaminonaphthyl, 2,6-diaminonaphthyl, 2,7-diaminonaphthyl, 2,8-diamine Naphthyl, 1,2-bis(4-aminophenyl)ethane, 1,2-bis(3-aminophenyl)ethane, 1,3-bis(4-aminophenyl)propane , 1,3-bis(3-aminophenyl)propane, 1,4-bis(4-aminophenyl)butane, 1,4-bis(3-aminophenyl)butane, bis ( 3,5-Diethyl-4-aminophenyl)methane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1 , 4-bis(4-amine Phenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminobenzyl)benzene, 1,3-bis(4-aminophenoxy) Benzene, 4,4'-[1,4-phenylenebis(methyl)diphenylamine, 4,4'-[1,3-phenylenebis(methyl)diphenylamine, 3, 4'-[1,4-phenylenebis(methyl)diphenylamine, 3,4'-[1,3-phenylenebis(methyl)diphenylamine, 3,3'-[ 1,4-phenylphenylbis(methyl)diphenylamine, 3,3'-[1,3-phenylenebis(methyl)diphenylamine, 1,4-phenylene bis[( 4-aminophenyl)methanone], 1,4-phenylene bis[(3-aminophenyl)methanone], 1,3-phenylene bis[(4-aminophenyl)methyl Ketone], 1,3-phenylene bis[(3-aminophenyl)methanone], 1,4-phenylene bis(4-aminobenzoate), 1,4-phenylene Bis(3-aminobenzoic acid ester), 1,3-phenylene bis(4-aminobenzoate), 1,3-phenylphenylbis(3-aminobenzoate), Bis(4-aminophenyl)terephthalate, bis(3-aminophenyl)terephthalate, bis(4-aminophenyl)isophthalate, bis( 3-aminophenyl)isophthalate, N,N'-(1,4-phenylene)bis(4-aminobenzamide), N,N'-(1,3- Phenyl) bis(4-aminobenzamide), N,N'-( 1,4-phenylene) bis(3-aminobenzamide), N,N'-(1,3-phenylene)bis(3-aminobenzamide), N,N' - bis(4-aminophenyl)terephthalamide, N,N'-bis(3-aminophenyl)terephthalamide, N,N'-bis(4-aminobenzene Isophthalamide, N,N'-bis(3-aminophenyl)isophthalamide, 9,10-bis(4-aminophenyl)anthracene, 4,4'- Bis(4-aminophenoxy)diphenylanthracene, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[4-(4- Aminophenoxy)phenyl]hexafluoropropane, 2,2'-bis(4-aminophenyl)hexafluoropropane, 2,2'-bis(3-aminophenyl)hexafluoropropane, 2 , 2'-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2'-bis(4-aminophenyl)propane, 2,2'-bis(3-aminobenzene) Propane, 2,2'-bis(3-amino-4-methylphenyl)propane, 3,5-diaminobenzoic acid, 2,5-diaminobenzoic acid, 1,3-double (4-Aminophenoxy)propane, 1,3-bis(3-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,4-double ( 3-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,5-bis(3-aminophenoxy)pentane, 1,6-double (4-aminophenoxy)hexane 1,6-bis(3-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1,7-(3-aminophenoxy)heptane 1,8-bis(4-aminophenoxy)octane, 1,8-bis(3-aminophenoxy)octane, 1,9-bis(4-aminophenoxy)anthracene Alkane, 1,9-bis(3-aminophenoxy)decane, 1,10-(4-aminophenoxy)decane, 1,10-(3-aminophenoxy)decane 1,11-(4-Aminophenoxy)undecane, 1,11-(3-aminophenoxy)undecane, 1,12-(4-aminophenoxy)12 Aromatic diamines such as alkane and 1,12-(3-aminophenoxy)dodecane, bis(4-aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl)methane Equivalent alicyclic diamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7- Diamino heptane, 1,8-diaminooctane, 1,9-diaminodecane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12 An aliphatic diamine such as diaminododecane.

The other diamines can be used in one type or in a mixture of two or more types in accordance with characteristics such as liquid crystal alignment property, tilt angle, voltage holding property, and storage charge when used as a liquid crystal alignment film.

The tetracarboxylic dianhydride which reacts with the above-mentioned diamine component in the synthesis of poly-proline is not specifically limited. Specific examples thereof include pyromellitic acid, 2,3,6,7-naphthyltetracarboxylic acid, 1,2,5,6-naphthyltetracarboxylic acid, and 1,4,5,8-naphthyltetracarboxylic acid. , 2,3,6,7-decanetetracarboxylic acid, 1,2,5,6-nonanedicarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3' , 4-biphenyltetracarboxylic acid, bis(3,4-dicarboxyphenyl)ether, 3,3',4,4'-benzophenonetetracarboxylic acid, bis(3,4-dicarboxybenzene Base, bis(3,4-dicarboxyphenyl)methane, 2,2-bis(3,4-dicarboxyphenyl)propane, 1,1,1,3,3,3-hexafluoro-2 , 2-bis(3,4-dicarboxyphenyl)propane, bis(3,4-dicarboxyphenyl)dimethyl decane, bis(3,4-dicarboxyphenyl)diphenyl decane, 2, 3,4,5-pyridinetetracarboxylic acid, 2,6-bis(3,4-dicarboxyphenyl)pyridine, 3,3',4,4'-diphenylphosphonium tetracarboxylic acid, 3,4, 9,10-decanetetracarboxylic acid, 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid, oxydi-phthalic acid, 1,2,3,4 - cyclobutane tetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,3,4-tetramethyl- 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,3-dimethyl-1,2, 3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cycloheptanetetracarboxylic acid, 2,3,4,5-tetrahydrofuran Carboxylic acid, 3,4-dicarboxy-1-cyclohexyl succinic acid, 2,3,5-tricarboxycyclopentyl acetic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1- Naphthyl succinic acid, bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic acid, bicyclo[4,3,0]nonane-2,4,7,9-tetracarboxylic acid Bicyclo[4,4,0]decane-2,4,7,9-tetracarboxylic acid, bicyclo[4,4,0]nonane-2,4,8,10-tetracarboxylic acid, tricyclo[ 6.3.0.0<2,6>]undecane-3,5,9,11-tetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, 4-(2,5-di-sided oxytetrahydrofuran -3-yl)-1,2,3,4-tetrahydronaphthyl-1,2-dicarboxylic acid, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetra Carboxylic acid, 5-(2,5-di-sided oxytetrahydrofuran)-3-methyl-3-cyclohexane-1,2-dicarboxylic acid, tetracyclo[6,2,1,1,0,2, 7] dodecane-4,5,9,10-tetracarboxylic acid, 3,5,6-tricarboxynorbornane-2:3,5:6 dicarboxylic acid, 1,2,4,5-ring Hexanetetracarboxylic acid and the like. Of course, the tetracarboxylic dianhydride also has one type or two or more types in combination with the liquid crystal alignment property, the voltage retention property, and the storage charge when the liquid crystal alignment film is used.

When a polyamine acid is obtained by the reaction of a diamine component and a tetracarboxylic dianhydride, a well-known synthetic method can be used. A method of reacting a diamine component with a tetracarboxylic dianhydride in an organic solvent is generally employed. The reaction of the diamine component with the tetracarboxylic dianhydride is relatively easy to carry out in an organic solvent, and it is advantageous in that no by-product is produced.

The organic solvent to be used in the above reaction is not particularly limited as long as it is a polylysine which is produced by dissolution. Further, even if it is an organic solvent which does not dissolve polyamic acid, it can be used after being mixed with the above solvent in the range in which the produced polyamic acid is not precipitated. Further, since the water in the organic solvent does not inhibit the polymerization reaction and becomes a polylysine which is formed by hydrolysis, it is preferred that the organic solvent be dried by dehydration. Examples of the organic solvent used in the reaction include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide, and N-methylmethyl. Indoleamine, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-di Methylpropane decylamine, N-methyl caprolactam, dimethyl hydrazine, tetramethyl urea, pyridine, dimethyl hydrazine, hexamethyl hydrazine, γ-butyrolactone, isopropanol, A Oxymethylpentanol, dipentene, ethyl amyl ketone, methyl decyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropanone, methyl sarsulu, ethyl 赛路Sue, methyl sarbuta acetate, ethylene glycol dibutyl ether acetate, ethylene glycol diethyl ether acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol Acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol - tert-butyl ether, two Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol, diethylene glycol monoacetate, Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate single Ethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3 - methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methyl cyclohexene, Propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, Ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, 3-ethoxypropane Acid methyl ethyl ester, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, 3-methoxypropionic acid Ester, diglyme, 4-hydroxy-4-methyl-2-pentanone, 2-ethyl-1-hexanol Wait. These organic solvents may be used singly or in combination.

When the diamine component and the tetracarboxylic dianhydride component are reacted in an organic solvent, a solution in which the diamine component is dispersed or dissolved in an organic solvent is stirred, and the tetracarboxylic dianhydride is directly or dispersed or dissolved in an organic solvent, and then added. In the method, a method of adding a diamine component to a solution in which a tetracarboxylic dianhydride is dispersed or dissolved in an organic solvent, a method of mutually adding a tetracarboxylic dianhydride and a diamine component, and the like may be mentioned, and any of these methods may be used. Can be. Further, when the tetracarboxylic dianhydride or the diamine component is formed of a plurality of compounds, the reaction may be carried out in a state of being mixed in advance, or the reaction may be carried out in a separate order, and the low molecular weight bodies of the respective reactions may be subjected to a mixing reaction. After that, it is a high molecular weight body.

The temperature at which the diamine component and the tetracarboxylic dianhydride component are reacted may be any temperature, for example, -20 ° C to 150 ° C, preferably -5 ° C to 100 ° C. Further, the reaction can be carried out at any concentration. For example, the total amount of the diamine component and the tetracarboxylic dianhydride component of the reaction liquid is preferably from 1 to 50% by mass, preferably from 5 to 30% by mass.

In the above polymerization reaction, the total molar ratio of the tetracarboxylic dianhydride component to the total number of moles of the diamine component is an arbitrary value depending on the molecular weight of the obtained polyamic acid. As in the case of the general polycondensation reaction, the closer to the molar ratio of 1.0, the larger the molecular weight of the produced polyamine. A preferred range is from 0.8 to 1.2.

The method for synthesizing the polyaminic acid used in the present invention is not limited to the above method, and similarly to the general method for synthesizing poly-proline, a tetracarboxylic or tetracarboxylic acid having a corresponding structure is used instead of the above tetracarboxylic dianhydride. A tetracarboxylic acid derivative such as a dihalide can be obtained by a known method to obtain a corresponding polyamine.

The method of the polyimine which bismuthizes the said poly lysine is the heat-imidation of the solution of the poly phthalic acid, and the catalyst of the solution of the poly phthalic acid. The catalyst is imidized. Moreover, the ruthenium imidization ratio of the polyamidene to the polyimine is not necessarily 100%.

The temperature at which the polyaminic acid is thermally imidized in the solution is from 100 ° C to 400 ° C, preferably from 120 ° C to 250 ° C, and the water formed by the hydrazine imidization reaction is excluded from the system. It is better to carry out the outside.

The catalyst oxime imidization of poly-proline is carried out by adding a basic catalyst and an acid anhydride to a solution of polyglycine, and stirring can be carried out at -20 to 250 ° C, preferably at 0 to 180 ° C. The amount of the basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, and the amount of the acid anhydride is 1 to 50 moles, preferably 3 to the amidate group. 30 moles. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is preferred because it has a moderate alkalinity for the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic dianhydride. Among them, when acetic anhydride is used, purification after completion of the reaction is preferred, which is preferable. The imidization ratio of the imidization by the catalyst oxime can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time.

Further, the polyphthalate is a reaction of a tetracarboxylic acid diester dichloride with a diamine similar to the synthesis of the above polyamic acid, or a tetracarboxylic acid diester having the same composition as that of the above polyamic acid. The diamine can be produced by reacting it in the presence of a suitable condensing agent or a base. Alternatively, polylysine may be synthesized in advance by the above method, and a carboxylic acid in valeric acid may be esterified by a polymer reaction to obtain a carboxylic acid. Specifically, for example, the tetracarboxylic acid diester dichloride and the diamine can be carried out in the presence of a base and an organic solvent at -20 ° C to 150 ° C, preferably at 0 ° C to 50 ° C for 30 minutes. After 24 hours, it is preferred to synthesize a polyphthalate after a reaction of 1 hour to 4 hours. On the other hand, when the polyglycolate is heated at a high temperature, even if it is closed by promoting the dealcoholization, a polyimine can be obtained.

The polyimine precursor or the like which is formed by the polyimine acid precursor, the polyamidomate or the like, or the polyamidene precursor, or the polyimide In the case of quinone imine, the reaction solution may be placed in a weak solvent to precipitate. Examples of the weak solvent used for precipitation include methanol, acetone, hexane, ethylene glycol dibutyl ether, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water, and the like. The polymer precipitated by the weak solvent is recovered by filtration, and then dried under normal pressure or under reduced pressure at normal temperature or under reduced pressure. Further, the precipitate-recovered polymer is redissolved in an organic solvent, and the operation of reprecipitation recovery is repeated 2 to 10 times to reduce impurities in the polymer. Examples of the weak solvent at this time include alcohols, ketones, hydrocarbons, and the like. When three or more kinds of weak solvents selected from the above are used, the purification efficiency can be further improved, which is preferable.

Further, a method of producing a polyoxyalkylene having a side chain in which the liquid crystal is aligned vertically is not particularly limited, and for example, a condensation product of an alkoxysilane or an alkoxysilane can be produced by polycondensation. Further, the condensate of alkoxydecane is a polymer of alkoxydecane or the like, and a polymer of alkoxydecane. As the alkoxydecane, only alkoxysilane having a side chain in which a liquid crystal is aligned is used, and a polyoxyalkylene having a side chain in which a liquid crystal is aligned perpendicularly can be formed. Further, when the polyoxyalkylene having a vertical alignment of the liquid crystal contains a photoreactive side chain, an alkoxysilane having a photoreactive side chain or the condensed body may be used.

Examples of the alkoxydecane having a side chain in which the liquid crystal is aligned perpendicularly include a long-chain alkyl group, a group having a ring structure or a branched structure in the middle of a long-chain alkyl group, a hydrocarbon group such as a steroid group, or a hydrogen group of these groups. The group in which a part or all of the fluorine atom is substituted by the fluorine atom is, for example, an alkoxy decane represented by the above formula (7). For the above formula (7), R ¹¹ is preferably an alkyl group or a fluoroalkyl group, and particularly preferably an alkyl group. Further, R ¹² is preferably an alkyl group having 1 to 5 carbon atoms, particularly preferably an alkyl group having 1 to 3 carbon atoms. Preferably, R ¹² is a methyl group or an ethyl group.

Specific examples of the alkoxydecane represented by the above formula (7) include octyltrimethoxydecane, octyltriethoxydecane, decyltrimethoxydecane, and decyltriethoxydecane. Dodecyltrimethoxydecane, dodecyltriethoxydecane, cetyltrimethoxydecane, cetyltriethoxydecane, heptadecyltrimethoxydecane,heptadecane Triethoxy decane, octadecyl trimethoxy decane, octadecyl triethoxy decane, nonadecyl trimethoxy decane, nonadecyl triethoxy decane, undecyl three Ethoxy decane, undecyltrimethoxy decane, 21-docosyltriethoxydecane, tridecafluorooctyltrimethoxydecane, tridecafluorooctyltriethoxydecane, seventeen Fluorinyltrimethoxydecane, heptadecafluorodecyltriethoxydecane, isooctyltriethoxydecane,phenethyltriethoxydecane,pentafluorophenylpropyltrimethoxydecane, (1 -naphthyl)triethoxydecane, (1-naphthyl)trimethoxydecane, and the like. Also included are octyltrimethoxydecane, octyltriethoxydecane, decyltrimethoxydecane, decyltriethoxydecane, dodecyltrimethoxydecane, dodecyltriethoxy Decane, cetyltrimethoxydecane, cetyltriethoxydecane, heptadecyltrimethoxydecane, heptadecyltriethoxydecane,octadecyltrimethoxydecane, ten Octacyclotriethoxydecane, nonadecyltrimethoxynonane, nonadecyltriethoxydecane, undecyltriethoxydecane or undecyltrimethoxydecane, triethoxy Preference is given to vinylidene oxide, trimethoxyvinyl decane, triethoxyallyl decane, trimethoxyallyl decane, triethoxystyrene decane and trimethoxystyrene decane.

Examples of the alkoxydecane having another side chain in which the liquid crystal is aligned perpendicularly include an alkoxydecane having a side chain represented by the above formula (a).

The alkoxy decane represented by the above formula (7) or an alkoxy decane having a side chain represented by the above formula (a) and the like having an alkoxy decane in which a liquid crystal is aligned in a vertical side chain, in order to obtain a good liquid crystal alignment property, The total alkoxy decane to be used for obtaining the polyoxyalkylene is preferably 0.1 mol% or more, more preferably 0.5 mol% or more, still more preferably 1 mol% or more. Further, the liquid crystal alignment film to be formed is preferably 30 mol% or less, preferably 22 mol% or less, in order to obtain sufficient curing properties.

Further, examples of the alkoxydecane having a photoreactive side chain include a vinyl group, a propenyl group, a methacryl group, an allyl group, a styryl group, a cinnamyl group, a chalcone group, a coumarin group, and a horse. Examples of the side chain of a photoreactive group such as a decylamine, an epoxy group, a vinyloxy group, or a propyleneoxy group include, for example, a photoreactive basic body or an alkyl group in which hydrogen is replaced by a photoreactive group. Specific examples of the alkoxydecane having a chain include an alkoxydecane represented by the above formula (8). In the above formula (8), the hydrogen substituted by R ¹³ is one or more, preferably one. Further, the alkyl group of R ¹³ preferably has 1 to 30 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms. R ¹⁴ is preferably an alkyl group having 1 to 5 carbon atoms, particularly preferably an alkyl group having 1 to 3 carbon atoms. More preferably, R ¹⁴ is a methyl group or an ethyl group.

Specific examples of the alkoxydecane represented by the above formula (8) include, for example, 3-methacryloxypropyltrimethoxydecane, 3-methylpropoxypropyltriethoxydecane, and A. Propenyloxymethyltrimethoxydecane, methacryloxymethyltriethoxydecane, 3-propoxypropyltrimethoxydecane, 3-propenyloxypropyltriethoxydecane, propylene Oxyethyltrimethoxydecane, propyleneoxyethyltriethoxydecane, and the like.

Examples of the alkoxysilane having a side chain having another photoreactivity include an alkoxydecane having a side chain represented by the above formula (b).

Alkoxy decane having a photoreactive side chain such as an alkoxy decane represented by the above formula (8) or an alkoxy decane having a side chain represented by the above formula (b), which is to be sufficiently cured to form a liquid crystal alignment film It is preferable that 60% by mole or less of the total alkoxy decane to be used for obtaining a polyoxyalkylene is used, but when it is contained at 60% by mole or more from the viewpoint of vertical alignment, there is a concern that it is lowered. It is preferably 20 to 50 mol%.

Also, other alkoxy decanes can be used. The other alkoxy decane is an alkoxy decane represented by the following formula (9). By using one or a plurality of alkoxysilanes represented by the following formula (9), the adhesion to the substrate and the affinity with the liquid crystal molecules can be improved.

(R ¹⁵ ) _n Si(OR ¹⁶ ) _4-n (9)

(In the formula (9), R ¹⁵ may be a hydrocarbon group having 1 to 6 carbon atoms which may be substituted by hydrogen or a hetero atom, a halogen atom, an amine group, a glycidoxy group, a thiol group, an isocyanate group or a guanidino group, and R ¹⁶ An alkyl group having 1 to 5 carbon atoms, and n is an integer of 0 to 3)

Specific examples of the alkoxydecane of the above formula (9) include, when R ¹⁵ is hydrogen, trimethoxy decane, triethoxy decane, tripropoxy decane, and tributoxy decane.

Further, the alkoxydecane of the above formula (9) may have a carbon number of 1 as a substituent of R ^{15 which} may be substituted by a hetero atom, a halogen atom, an amine group, a glycidoxy group, a thiol group, an isocyanate group or a guanidino group. Specific examples of the hydrocarbon group of 6 include methyltrimethoxydecane, methyltriethoxydecane, ethyltrimethoxydecane, ethyltriethoxydecane, propyltrimethoxydecane, and propyl. Triethoxy decane, methyl tripropoxy decane, 3-aminopropyl trimethoxy decane, 3-aminopropyl triethoxy decane, N-2 (aminoethyl) 3-amino group Propyltriethoxydecane, N-2 (aminoethyl) 3-aminopropyltrimethoxydecane, 3-(2-aminoethylaminopropyl)trimethoxydecane, 3-( 2-Aminoethylaminopropyl)triethoxydecane, 2-aminoethylaminomethyltrimethoxydecane, 2-(2-aminoethylthioethyl)triethoxydecane , 3-hydrothiopropyltriethoxydecane, thiomethylmethyltrimethoxydecane, 3-isocyanatepropyltriethoxydecane, trifluoropropyltrimethoxydecane, chloropropyltriethoxy Base decane, bromopropyltriethoxy decane, 3-hydrothiopropyl Trimethoxy decane, dimethyl diethoxy decane, dimethyl dimethoxy decane, diethyl diethoxy decane, diethyl dimethoxy decane, diphenyl dimethoxy decane, Diphenyldiethoxydecane, 3-aminopropylmethyldiethoxydecane, 3-aminopropyldimethylethoxydecane, trimethylethoxydecane, trimethylmethoxy Basear, γ-ureidopropyltriethoxydecane, γ-ureidopropyltrimethoxydecane, γ-ureidopropyltripropoxydecane, and the like.

For the alkoxydecane represented by the above formula (9), the alkoxydecane wherein n is 0 is a tetraalkoxydecane. The tetraalkoxy decane is preferably used because it is easily condensed with the alkoxy decane represented by the above formula (7) and the alkoxy decane represented by the above formula (8). As the alkoxydecane in which n in the above formula (9) is 0, tetramethoxynonane, tetraethoxydecane, tetrapropoxydecane or tetrabutoxydecane is preferable, particularly tetramethoxy. Preferably, decane or tetraethoxy decane is preferred.

When the alkoxydecane represented by the above formula (9) is used, the amount of the alkoxydecane represented by the above formula (9) is 10 to 99.8 in terms of the total alkoxydecane used to obtain the polyoxyalkylene. The ear % is preferably, preferably from 35 to 96.9 mole %.

As a method of polycondensing the alkoxysilane or the condensate, for example, a method of hydrolyzing and condensing an alkoxysilane or a condensate thereof in a solvent such as an alcohol or a glycol may be mentioned. At this time, the hydrolysis/condensation reaction may be either partial hydrolysis or complete hydrolysis. In the case of complete hydrolysis, it is theoretically possible to add 0.5 times mole of water of the alkoxysilane or a total alkoxy group of the condensate thereof, and it is preferred to add an excess amount of water more than 0.5 times mole. In the present invention, the amount of water used in the above reaction can be appropriately selected in accordance with the necessity, and it is usually 0.5 to 2.5 times moles of the total alkoxy group in the alkoxydecane.

Further, for the purpose of promoting hydrolysis and condensation, an acid such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid, maleic acid or fumaric acid is used; ammonia, methylamine, ethylamine, ethanolamine, triethylamine Such as alkali; metal salts such as hydrochloric acid, sulfuric acid, nitric acid; etc.; Further, the solution of the alkoxysilane can be dissolved by heating to further promote the hydrolysis and the condensation reaction to be general. At this time, the heating temperature and the heating time can be appropriately selected in accordance with the needs. For example, heating at 50 ° C for 24 hours, stirring or refluxing for 1 hour, heating, stirring, etc. may be mentioned.

Further, as another method, for example, a polycondensation method of heating a mixture of alkoxysilane or a condensate thereof, a solvent, and oxalic acid can be mentioned. Specifically, a method in which oxalic acid is added to an alcohol to form an alcohol solution of oxalic acid, and then the solution is heated to mix an alkoxysilane or a condensate thereof. In this case, the amount of oxalic acid to be used is preferably 0.2 to 2 mols for the peralkoxy group 1 mol having an alkoxydecane or a condensate thereof. The heating in this method can be carried out at a liquid temperature of 50 to 180 °C. Preferably, the method of heating for several tenths to ten hours under reflux is caused without causing evaporation or volatilization of the liquid.

When a polyoxyalkylene oxide is obtained, when a plurality of alkoxysilanes or a condensate thereof are used, the alkoxysilane or a condensate thereof may be mixed in advance to form a mixture, or a plurality of alkoxysilanes or condensates thereof may be used. The order can also be mixed.

The solvent used in the condensation polymerization of the alkoxysilane or the condensate thereof (hereinafter also referred to as a polymerization solvent) is not particularly limited as long as it can dissolve the alkoxysilane or a condensate thereof. Further, even when the alkoxysilane or the condensate thereof is not dissolved, the polycondensation reaction with the alkoxysilane or the condensate thereof may be simultaneously dissolved. In general, since an alcohol is formed by a polycondensation reaction of an alkoxysilane or a condensate thereof, an organic solvent having good compatibility with an alcohol, a glycol, a glycol ether or an alcohol is used.

Specific examples of the polycondensation solvent include alcohols such as methanol, ethanol, propanol, butanol, and diacetone alcohol: ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, hexanediol, and 1,3. -propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol , 1,4-pentanediol, 1,5-pentanediol, 2,4-pentanediol, 2,3-pentanediol, 1,6-hexanediol, etc.: glycol monomethyl Ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether , ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol II Methyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol Glycol ethers such as monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, N- Base-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, γ-butyrolactone, dimethyl hydrazine, tetramethylurea, hexamethylphosphonium Triamine, m-cresol and the like. The polymerization solvent can be used after mixing a plurality of kinds.

In the polymerization solution of the polyoxane obtained by the above method (hereinafter also referred to as a polymerization solution), the argon atom of the peralkoxy decane used as the raw material is converted into the concentration of SiO ₂ (hereinafter referred to as SiO ₂ conversion concentration). It is preferably 20% by mass or less, preferably 5 to 15% by mass. By arbitrarily selecting this concentration range, formation of a gel can be suppressed to obtain a homogeneous solution.

Moreover, in the present invention, the polymerization solution obtained by the above method may be directly contained in the liquid crystal alignment agent, or the polydecane oxide may be precipitated as a solid and further contained in the liquid crystal alignment agent, and the solution obtained by the above method may be concentrated or The solvent is diluted or substituted with another solvent to be contained in the liquid crystal alignment agent. At this time, the solvent to be used (hereinafter also referred to as an additive solvent) may be the same as the polymerization solvent, or may be another solvent. The additive solvent is not particularly limited as long as it can be uniformly dissolved, and a plurality of types can be used singly or arbitrarily. Specific examples of the solvent to be added include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; and methyl acetate, ethyl acetate, and ethyl lactate. Esters. These solvents are those that improve the viscosity of the liquid crystal alignment agent or apply the liquid crystal alignment agent to the substrate by spin coating, stencil printing, jet printing, or the like.

As described above, the liquid crystal alignment agent of the present invention may have only the polymerizable compound represented by the above formula (1) and a polymer and a solvent which form a liquid crystal alignment film perpendicular to the liquid crystal alignment. The compounding ratio is not particularly limited. The content of the polymerizable compound represented by the formula (1) is preferably from 1 to 50 parts by mass, preferably from 5 to 30 parts by mass, per 100 parts by mass of the polymer which forms the liquid crystal alignment film which is perpendicular to the liquid crystal. Further, the content of the polymer contained in the liquid crystal alignment film in which the liquid crystal alignment agent is formed in the liquid crystal alignment agent is preferably 1% by mass to 20% by mass, more preferably 3% by mass to 15% by mass, particularly preferably 3 Mass% to 10% by mass.

Further, the liquid crystal alignment agent of the present invention may contain other polymers in addition to the polymer which forms the liquid crystal alignment film which is perpendicular to the liquid crystal alignment. In this case, the content of the other polymer in the entire polymer component is preferably 0.5% by mass to 15% by mass, preferably 1% by mass to 10% by mass.

The molecular weight of the polymer having a liquid crystal alignment agent is determined by GPC (Gel Permeation Chromatography) method in consideration of the strength of the liquid crystal alignment film obtained by coating the liquid crystal alignment agent, the workability at the time of coating film formation, and the uniformity of the coating film. The weight average molecular weight is preferably 5,000 to 1,000,000, preferably 10,000 to 150,000.

The solvent to be contained in the liquid crystal alignment agent is not particularly limited, and only the polymerizable compound represented by the above formula (1) or a polymer such as a polymer which forms a liquid crystal alignment film perpendicular to the liquid crystal may be dissolved or dispersed. For example, a polymerization solvent or an additive solvent exemplified in the synthesis of the organic solvent or the polysiloxane which is exemplified in the synthesis of the polyamic acid may be mentioned. Among them, N-methyl-2-pyrrolidone, γ-butyrolactone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N - Dimethylpropane decylamine is preferred from the viewpoint of solubility. Of course, it is also possible to use a mixed solvent of two or more types.

Further, it is preferred to use a solvent which improves the uniformity or smoothness of the coating film in a solvent having a high solubility in the component contained in the liquid crystal alignment agent. Examples of the solvent for improving the uniformity or smoothness of the coating film include isopropyl alcohol, methoxymethylpentanol, methyl sarbuta, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, and methyl group.赛路苏acetate, ethylene glycol dibutyl ether acetate, ethylene glycol diethyl ether acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol , ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol - third Butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate Methyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetic acid Ester monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl Butyl ether, Isobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methyl cyclohexene, propyl ether, hexyl ether, n-hexane, n-pentane, n-octane , diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, 3-methoxy propyl Methyl ester, methyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid Ester, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy 2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol , 2-(2-ethoxypropoxy)propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, 2-ethyl- 1-hexanol and the like. These solvents can be mixed in a plurality of types. When these solvents are used, the total amount of the solvent contained in the liquid crystal alignment agent is preferably from 5 to 80% by mass, preferably from 20 to 60% by mass.

The liquid crystal alignment agent may contain components other than the above. As such an example, a compound which improves the film thickness uniformity or surface smoothness when a liquid crystal alignment agent is applied, and a compound which improves the adhesion between the liquid crystal alignment film and the substrate can be mentioned.

Examples of the compound for improving film thickness uniformity or surface smoothness include a fluorine-based surfactant, a polyfluorene-based surfactant, and a nonionic surfactant. More specifically, Eftop EF301, EF303, EF352 (made by TOHKEM PRODUCTS CORP), Megafac F171, F173, R-30 (made by Dainippon Ink Co., Ltd.), Fluorad FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), Asahiguard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (made by Asahi Glass Co., Ltd.). When the surfactant is used, the use ratio is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass of the total amount of the polymer contained in the liquid crystal alignment agent.

Specific examples of the compound which improves the adhesion between the liquid crystal alignment film and the substrate include a compound containing a functional decane or a compound containing an epoxy group. Examples thereof include 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, and 2-aminopropyltriethoxydecane. N-(2-Aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-anthracene Ureapropyltrimethoxydecane, 3-guanidinopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-aminopropyl Triethoxy decane, N-triethoxymercaptopropyltriethylamine, N-trimethoxydecylpropyltriethylamine, 10-trimethoxydecyl-1, 4,7-triazadecane, 10-triethoxyindolyl-1,4,7-triazadecane, 9-trimethoxyindolyl-3,6-diazaindolyl acetic acid Ester, 9-triethoxyindolyl-3,6-diazaindolyl acetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3-amine Propyl triethoxy decane, N-phenyl-3-aminopropyl trimethoxy decane, N-phenyl-3-aminopropyl triethoxy decane, N-bis (oxyethyl) )-3-aminopropyltrimethoxydecane, N-bis(oxyethyl)-3- Aminopropyltriethoxydecane, ethylene glycol propylene oxide ether, polyethylene glycol propylene oxide ether, propylene glycol propylene oxide ether, tripropylene glycol propylene oxide ether, polypropylene glycol propylene oxide ether, neopentyl Alcohol propylene oxide, 1,6-hexanediol propylene oxide ether, glycerin propylene oxide ether, 2,2-dibromoneopentyl glycol propylene oxide ether, 1,3,5,6-tetrapropylene oxide Base-2,4-hexanediol, N,N,N',N'-tetraoxypropylene-m-xylenediamine, 1,3-bis(N,N-propylene oxide aminomethyl) Cyclohexane, N,N,N',N'-tetrapropenyl-4,4'-diaminodiphenylmethane, 3-(N-allyl-N-propylene oxide)aminopropyl Trimethoxy decane, 3-(N,N-propylene oxide) aminopropyltrimethoxydecane, and the like. Further, in order to further increase the film strength of the liquid crystal alignment film, a phenol compound such as 2,2'-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane or tetrakis(methoxymethyl)bisphenol may be added. . When these compounds are used, the amount of the epoxy group-containing compound is preferably from 0.1 to 30 parts by mass, preferably from 1 to 20 parts by mass, per 100 parts by mass of the total amount of the polymer contained in the liquid crystal alignment agent. .

Further, in the liquid crystal alignment agent, the above-mentioned other components of the dielectric material or the conductive material for the purpose of changing the electrical properties such as the dielectric constant or the conductivity of the liquid crystal alignment film may be added to the extent that the effects of the present invention are not impaired.

Further, the liquid crystal alignment agent may contain inorganic fine particles, a metal oxyalkylene oligomer, a metal oxyalkylene polymer, a coating agent, a surfactant, and the like.

As the inorganic fine particles, fine particles such as cerium oxide fine particles, alumina fine particles, titania fine particles or magnesium fluoride fine particles are preferred, and in particular, a colloidal solution state is preferred. The colloidal solution may be a dispersion of inorganic fine particles in a dispersion medium, or may be a commercial colloidal solution. In the present invention, by containing inorganic fine particles, the surface shape and other functions of the formed cured film can be imparted. The inorganic particles have an average particle diameter of 0.001 to 0.2 μm, more preferably 0.001 to 0.1 μm. When the average particle diameter of the inorganic fine particles exceeds 0.2 μm, the transparency of the cured film formed using the prepared coating liquid may be lowered.

Examples of the dispersion medium of the inorganic fine particles include water and an organic solvent. The colloidal solution is preferably adjusted to have a pH or pKa of from 1 to 10 from the viewpoint of stability of the coating liquid for forming a film. More preferably 2 to 7.

Examples of the organic solvent used as the dispersion medium for the colloidal solution include methanol, propanol, butanol, ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, diethylene glycol, dipropylene glycol, and B. Alcohols such as diol monopropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene; dimethylformamide, dimethylacetamide, N- An amide such as methylpyrrolidone; an ester such as ethyl acetate, butyl acetate or γ-butyrolactone; or an ether such as tetrahydrofuran or 1,4-dioxane. Among them, alcohols or ketones are preferred. These organic solvents may be used singly or in combination of two or more kinds as a dispersion medium.

As the metal oxyalkylene oligomer or the metal oxyalkylene polymer, a single or composite oxide precursor such as ruthenium, titanium, aluminum, ruthenium, osmium, iridium, tin, indium or zinc can be used. The metal oxyalkylene oligomer or the metal oxyalkylene polymer may be commercially available, or may be obtained by a usual method such as hydrolysis of a monomer such as a metal alkoxide, a nitrate, a hydrochloride or a carboxylate.

Specific examples of the metal oxyalkylene oligomer and the metal oxyalkylene polymer which are commercially available include methyl phthalate 51 manufactured by COLCOAT Co., Ltd., methyl citrate 53A, ethyl decanoate 40, and ethyl hydrazine. a titanyl oxide oligomer such as a buffer of a sulfonium oxide oligomer such as EMS-485 or SS-101 or a cesium alkoxide polymer or a titanium-n-butoxide oxide tetramer manufactured by Kanto Chemical Co., Ltd. These can be used individually or in mixture of 2 or more types.

Further, a coating agent, a surfactant, and the like can be used, and it is particularly preferable to use a product which is easy to start.

The method of adjusting the liquid crystal alignment agent of the present invention is not particularly limited. It may be a state in which the polymerizable compound represented by the above formula (1) is uniformly mixed, a polymer which forms a liquid crystal alignment film in which the liquid crystal is aligned, and a component which is added as necessary may be used. For example, in general, polyoxyalkylene is subjected to polycondensation in a solvent as described above, so that a solution of polyoxyalkylene can be used as it is, or a simple method of adding other components as necessary in a solution of polyoxyalkylene. The method of directly using the polymerization solution of polyoxyalkylene is the simplest method.

Further, when the content of the polymer which forms the liquid crystal alignment film which is perpendicular to the liquid crystal alignment in the liquid crystal alignment agent is adjusted, a polymerization solvent selected from the organic solvent or polysiloxane which is exemplified by the synthesis of the polyamic acid can be used. A solvent in which the solvent is added.

By applying the liquid crystal alignment agent onto a substrate and baking it, a liquid crystal alignment film in which liquid crystal alignment is perpendicular can be formed. Since the liquid crystal alignment agent of the present invention has the polymerizable compound represented by the above formula (1), the liquid crystal display element used in the obtained liquid crystal alignment film can be made to have a fast response speed.

For example, after the liquid crystal aligning agent of the present invention is applied onto a substrate, the cured film obtained by drying and drying after necessary may be used as a liquid crystal alignment film as it is. Further, the cured film may be rubbed, or irradiated with polarized light or light of a specific wavelength, or subjected to an ion beam or the like, or may be irradiated with UV as a PSA oriented film in a state where a voltage is applied to the liquid crystal display element after liquid crystal filling. It is especially useful as an oriented film for PSA.

In this case, the substrate to be used is not particularly limited as long as it is a substrate having high transparency, and a glass plate, a polycarbonate, a poly(meth)acrylate, a polyether oxime, a polyarylate, or a polyurethane can be used. , polyfluorene, polyether, polyether ketone, trimethylpentene, polyolefin, polyethylene terephthalate, (meth)acrylonitrile, cellulose triacetate, cellulose diacetate, acetate A plastic substrate such as ester cellulose. Further, when a substrate on which an ITO electrode or the like to be driven by liquid crystal is formed is used, it is preferable from the viewpoint of simplification of the process. Further, in the case of the reflective liquid crystal display device, only a single-sided substrate can be used, and an opaque material such as a germanium wafer can also be used. In this case, an optical material such as aluminum or the like, cellulose diacetate or acetic acid butyric acid can be used as the electrode. A plastic substrate such as ester cellulose.

The method of applying the liquid crystal alignment agent is particularly limited, and examples thereof include a printing method such as screen printing, offset printing, or stencil printing, a spraying method, a spraying method, a roll coating method, or dipping, roll coating, and slit coating. , spin coater, etc. From the viewpoint of productivity, a transfer printing method widely used in the industry is also applicable to the present invention.

Although the drying step after the application of the liquid crystal aligning agent is not necessary, the drying step is preferably performed when the time from the application to the baking is not constant for each substrate or when the film is not immediately baked after coating. This drying is not particularly limited as long as the drying means is such that the solvent is removed without deforming the shape of the coating film. For example, a method of drying at a temperature of 40 ° C to 150 ° C, preferably 60 ° C to 100 ° C, for 0.5 minutes to 30 minutes, preferably 1 minute to 5 minutes, may be mentioned.

The coating film formed by applying the liquid crystal alignment agent in the above method can be fired to form a cured film. The baking temperature of the coating film formed by coating the liquid crystal alignment agent is not limited, and can be carried out, for example, at any temperature of 100 to 350 °C. When the liquid crystal alignment agent is a polyimine precursor having a side chain having a vertical alignment of the liquid crystal or a polyimine obtained by imidating the polyimine precursor, preferably 120 ° C to 300 °C, more preferably 150 ° C ~ 250 ° C. Further, when the liquid crystal alignment agent contains polyoxyalkylene having a side chain in which the liquid crystal is aligned vertically, it is preferably 140 ° C to 300 ° C, more preferably 150 ° C to 230 ° C, still more preferably 160 ° C to 220 ° C. The firing can be carried out at any time from 5 minutes to 240 minutes. It is preferably from 10 minutes to 90 minutes, more preferably from 20 minutes to 90 minutes. The heating can be carried out by a generally known method, for example, in a hot plate, a hot air circulating furnace, an infrared oven, an IR oven, a conveyor belt furnace or the like.

The polyoxyalkylene in the liquid crystal alignment film is subjected to polycondensation in the firing step. However, in the present invention, it is not necessary to completely condense only without impairing the effects of the present invention. However, it is necessary to carry out the firing in a liquid crystal cell manufacturing process at a temperature higher than the heat treatment temperature such as curing of the sealant by 10 ° C or higher.

Further, the thickness of the liquid crystal alignment film obtained by firing is not particularly limited, and the reliability of the liquid crystal display device is easily obtained, and is preferably 5 nm or more, and more preferably 10 nm or more. Further, since the power consumption of the liquid crystal display element is not extremely large, the thickness of the liquid crystal alignment film is preferably 300 nm or less, more preferably 150 nm or less, and particularly preferably 100 nm or less.

On the other hand, in the liquid crystal display device of the present invention, after the liquid crystal alignment film is formed on the substrate by the above method, the liquid crystal cell is produced by a known method. Specific examples of the liquid crystal display device include the above-described liquid crystal alignment agent having the two substrates arranged in the opposite direction, the liquid crystal layer provided between the substrates, and the liquid crystal layer provided by the liquid crystal alignment agent of the present invention. A liquid crystal display element in which a liquid crystal cell of a liquid crystal alignment film is vertically aligned. Specifically, the liquid crystal alignment agent of the present invention is applied onto two substrates and fired to form a liquid crystal alignment film, and the two substrates are arranged such that the liquid crystal alignment film is in a relative direction, and the liquid crystal alignment film is held between the two substrates. In the liquid crystal layer, the liquid crystal layer is provided, and a liquid crystal layer is provided in contact with the liquid crystal alignment film, and a liquid crystal cell having a liquid crystal cell produced by applying ultraviolet rays to the liquid crystal alignment film and the liquid crystal layer is provided. By using the liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention, the liquid crystal alignment film and the liquid crystal layer are irradiated with ultraviolet rays while applying a voltage, and the polymerizable compound represented by the above formula (1) is polymerized to have an excellent response speed. Liquid crystal display element.

The substrate using the liquid crystal display element of the present invention is not particularly limited as long as it is a substrate having high transparency, and is generally a substrate on which a transparent electrode to be driven by a liquid crystal is formed on a substrate. As a specific example, the same substrate as described in the above liquid crystal alignment film can be mentioned. The liquid crystal display element of the present invention can be used as a liquid crystal alignment agent for forming a liquid crystal alignment film, and a polymerizable compound having the above formula (1) can be used. According to the liquid crystal alignment agent of the invention, a line/slot electrode pattern of, for example, 1 to 10 μm is formed on a single-sided substrate, and a structure in which a slit pattern or a protrusion pattern is not formed on the opposite direction substrate can also be used, by which the structure is The liquid crystal display element can achieve a high transmittance by simplifying the manufacturing process.

Further, for a high-function element such as a TFT type element, an element such as a transistor is formed between an electrode to be driven by a liquid crystal and a substrate.

In the case of a transmissive liquid crystal display device, a substrate as described above is generally used. In the reflective liquid crystal display device, an opaque substrate such as a germanium wafer can be used as the single-sided substrate. At this time, a material such as aluminum which can reflect light can be used in the electrode of the substrate.

The liquid crystal alignment film is formed by applying the liquid crystal alignment agent of the present invention to the substrate and firing it, and the details are as described above.

The liquid crystal material constituting the liquid crystal layer of the liquid crystal display device of the present invention is not particularly limited, and a liquid crystal material used in the past vertical alignment method can be used. For example, a negative liquid crystal such as MLC-6608 or MLC-6609 manufactured by Moker Corporation can be used.

A well-known method is mentioned as a method of holding this liquid crystal layer between two board|substrate. For example, a pair of substrates on which a liquid crystal alignment film is formed is prepared, and spacers such as beads are spread on the liquid crystal alignment film of one substrate, and the other substrate is bonded to the inside of the surface formed by the liquid crystal alignment film, and the liquid crystal is injected under reduced pressure and then sealed. The method can be mentioned. In addition, a pair of substrates formed by the liquid crystal alignment film are prepared, and a spacer such as a bead is spread on the liquid crystal alignment film of one of the substrates, and then the liquid crystal is dropped, and then the other substrate is bonded to the inside of the liquid crystal alignment film. The method of sealing can also produce a liquid crystal cell. The thickness of the spacer at this time is preferably from 1 to 30 μm, more preferably from 2 to 10 μm.

The step of producing a liquid crystal cell by applying a voltage to the liquid crystal alignment film and the liquid crystal layer while applying a voltage is, for example, an electric field applied to the liquid crystal alignment film and the liquid crystal layer after the input voltage between the electrodes provided on the substrate is applied, and the electric field is maintained. A method of irradiating ultraviolet rays. The voltage input between the electrodes is, for example, 5 to 30 Vp-p, preferably 5 to 20 Vp-p. The irradiation amount of the ultraviolet ray is, for example, 1 to 60 J, preferably 40 J or less, and the lower the amount of the ultraviolet ray irradiation, the lower the reliability of the member constituting the liquid crystal display element is suppressed, and the manufacturing efficiency can be improved by reducing the ultraviolet ray irradiation time. Therefore, it is better.

When the ultraviolet ray is applied to the liquid crystal alignment film and the liquid crystal layer while applying a voltage, the polymerizable compound represented by the above formula (1) reacts to form a polymer, and the tilt direction of the liquid crystal molecules is memorized by the polymer, thereby accelerating The response speed of the resulting liquid crystal display element.

In the above description, the liquid crystal display element produced by the liquid crystal alignment agent containing the liquid crystal alignment film containing the polymerizable compound represented by the above formula (1), the liquid crystal display element of the present invention may be such that the liquid crystal contains the above formula (1). The producer of the polymerizable compound shown. Specifically, the present invention includes a liquid crystal display device of a vertical alignment type of liquid crystal cells in which liquid crystal cells are provided with two substrates arranged in a relative direction, a liquid crystal layer disposed between the substrates, and a liquid crystal provided between the substrate and the liquid crystal layer. The liquid crystal cell of the alignment film is coated on two substrates by a liquid crystal alignment agent and fired to form a liquid crystal alignment film, and the two substrates are arranged such that the liquid crystal alignment film has a relative direction, and the two substrates are held between the two substrates. In the liquid crystal layer composed of the liquid crystal of the polymerizable compound represented by the above formula (1), a liquid crystal cell is produced by applying a voltage to the liquid crystal layer while irradiating ultraviolet rays, and a liquid crystal display element having a vertical alignment type of the liquid crystal cell is provided. The liquid crystal display device having the excellent response speed by polymerizing the polymerizable compound represented by the above formula (1) while applying a voltage to the liquid crystal layer of the polymerizable compound represented by the above formula (1) of the present invention .

The substrate is the same as the liquid crystal display element produced by containing the polymerizable compound represented by the above formula (1) on the liquid crystal alignment agent forming the liquid crystal alignment film.

In the liquid crystal alignment film, the polymerizable compound represented by the above formula (1) is removed by the liquid crystal alignment agent of the present invention, for example, a liquid crystal alignment agent is applied and then baked, and the same operation as the method for producing the liquid crystal alignment film is performed. Formed under.

Further, as the liquid crystal constituting the liquid crystal layer, a polymerizable compound containing the above formula (1) is used. The content of the polymerizable compound represented by the above formula (1) is, for example, 0.01 parts by mass to 0.10 parts by mass based on 100 parts by mass of the liquid crystal. When the content of the polymerizable compound contained in the liquid crystal is small, the response speed of the liquid crystal display element can be sufficiently improved by using the compound represented by the above formula (1) in the present invention. In addition, as the liquid crystal material, a liquid crystal material used in a past vertical alignment method such as a negative liquid crystal such as MLC-6608 or MLC-6609 manufactured by Mok Corporation can be used.

The method of holding the liquid crystal layer between the two substrates is the same as the liquid crystal display element produced by containing the polymerizable compound represented by the above formula (1) in the liquid crystal alignment agent forming the liquid crystal alignment film.

The liquid crystal cell is irradiated with ultraviolet rays to form a liquid crystal cell by applying a voltage. For example, a voltage is applied to the liquid crystal layer by an input voltage between the electrodes provided on the substrate, and a method of irradiating the ultraviolet light under the electric field is maintained. The voltage input between the electrodes is, for example, 5 to 30 Vp-p, preferably 5 to 20 Vp-p. The irradiation amount of the ultraviolet ray is, for example, 1 to 60 J, preferably 40 J or less, and the lower the amount of ultraviolet ray irradiation, the lower the reliability of the components constituting the liquid crystal display element, and the lower the reliability, and the manufacturing efficiency can be improved by reducing the ultraviolet ray irradiation time. Therefore, it is better.

When the ultraviolet ray is irradiated while applying a voltage to the liquid crystal layer, the polymerizable compound represented by the above formula (1) reacts to form a polymer, and the polymer is used, and the tilt direction of the liquid crystal molecules is memorized, whereby the obtained liquid crystal display element can be accelerated. The speed of response.

In addition, the liquid crystal display element produced by containing the polymerizable compound represented by the above formula (1) in the liquid crystal alignment agent forming the liquid crystal alignment film and containing the polymerizable compound represented by the above formula (1) in the liquid crystal may be used. In addition, a liquid crystal alignment film formed of a liquid crystal alignment agent containing the polymerizable compound represented by the above formula (1) may be used as the liquid crystal alignment film formed on the two substrates, but only one liquid crystal alignment film may be used. When the liquid crystal alignment agent containing the polymerizable compound represented by the above formula (1) is formed, the other liquid crystal alignment film may be formed by using a liquid crystal alignment agent not containing the polymerizable compound represented by the above formula (1).

Further, the liquid crystal alignment agent can be used not only as a liquid crystal alignment agent for a liquid crystal display element of a vertical alignment type such as a PSA liquid crystal display or an SC-PVA liquid crystal display, but also as a liquid crystal produced by rubbing treatment or photoalignment processing. Used for the purpose of the alignment film.

[Examples]

Hereinafter, the present invention will be described in more detail by way of Examples and Comparative Examples. However, the present invention is not limited thereto.

<Synthesis of Polymerizable Compound> (Example 1) Synthesis of polymerizable compound (RM1)

4,4'-bisphenol 6.7 g (35.9 mmol) and 2-(4-bromobutyl)-1,3-dioxolane 15.0 g (71.7 mmol) were placed in a 300 ml eggplant-shaped flask with a cooling tube. Further, 19.8 g (143 mmol) of potassium carbonate and 150 ml of acetone were used as a mixture, and the mixture was stirred at 60 ° C for 48 hours to carry out a reaction. After the completion of the reaction, the solvent was distilled off under reduced pressure to give a yellow, dry solid. Thereafter, the solid was mixed with 200 ml of water, and 80 ml of chloroform was added thereto and extracted. The extraction was carried out 3 times.

Anhydrous magnesium sulfate was added to the organic layer which was separated and dried, filtered, and the solvent was evaporated under reduced pressure to give a yellow solid. The solid was purified by recrystallization (hexane/chloroform = 4/1 (volume ratio)) to yield 14.6 g of white solid. The results of measurement of the obtained white solid by NMR are shown below. The obtained solid was dissolved in hydrazine-chloroform (CDCl ₃ ), and measured at 300 MHz using a nuclear magnetic resonance apparatus (manufactured by Diol Co., Ltd.). From the results, it was confirmed that the white solid was an intermediate compound (RM1-A) represented by the following reaction formula. The yield was 92%.

¹ H-NMR (CDCl ₃ ) δ: 1.65 (m, 4H), 1.74 (m, 4H), 1.87 (m, 4H), 3, 86 (m, 4H), 3.97 (m, 8H), 4.89 (t) , 2H), 6.92 (m, 4H), 7.44 (m, 4H).

Next, the above-obtained intermediate compound (RM1-A) 13.3 g (30 mmol), 2-(bromomethyl)acrylic acid 11.6 g (70 mmol), 10% hydrochloric acid (aq) were added to a 500 ml eggplant-shaped flask equipped with a cooling tube. 50 ml, 160 ml of tetrahydrofuran (THF), and 13.2 g (70 mmol) of tin (II) chloride were used as a mixture, and the mixture was stirred at 70 ° C for 20 hours to cause a reaction. After the completion of the reaction, the reaction mixture was filtered under reduced pressure and mixed with 200 ml of purified water, and then 100 ml of dichloroform was added and extracted. The extraction was carried out 3 times.

Anhydrous magnesium sulfate was added to the organic layer to be separated and dried, and the solvent was filtered off under reduced pressure to give a white solid. The solid was purified by recrystallization (hexane / chloroform = 2 / 1) to yield 9.4 g of white solid. The obtained white solid was measured by NMR in the same manner as above, and the polymerizable compound (RM1) represented by the following formula was confirmed for the white solid. The yield was 64%.

¹ H-NMR (CDCl ₃ ) δ: 1.69 (m, 12H), 2.61 (m, 2H), 3.09 (m, 2H), 4.40 (t, 4H), 4.57 (m, 2H), 5.64 (m, 2H) ), 6.24 (m, 2H), 6.92 (d, 4H), 7.45 (m, 4H).

(Example 2) Synthesis of polymerizable compound (RM2)

Add 4,4'-biphenyldicarboxyaldehyde 5.0g (23.8mmol), 2-(bromomethyl)acrylic acid 7.9g (47.6mmol), 10% hydrochloric acid (aq) to a 300ml eggplant-shaped flask with a cooling tube. 33 ml, 100 ml of tetrahydrofuran (THF), and 9.5 g (50 mmol) of tin (II) chloride were used as a mixture, and the mixture was stirred at 70 ° C for 20 hours to cause a reaction. After the completion of the reaction, the reaction solution was poured into 300 ml of pure water to obtain a white solid. The obtained solid was separated and purified by recrystallization (hexane / chloroform = 2 / 1) to afford 3.5 g of white solid. The solid compound was subjected to NMR measurement, and the polymerizable compound (RM2) represented by the following formula was confirmed for the white solid. The yield was 72%.

¹ H-NMR (CDCl ₃ ) δ: 2.99 (m, 2H), 3.42 (m, 2H), 5.60 (m, 2H), 5.74 (m, 2H), 6.36 (m, 2H), 7.42 (m, 4H) ), 7.60 (m, 4H).

(Comparative Example 1) Polymerizable Compound (RM3)

A polymerizable compound represented by the following formula is known as RM3.

(Example 3) Synthesis of polymerizable compound (RM4)

4,4'-bisphenol 11.2g (60mmol) and 2-(2-bromoethyl)-1,3-dioxol 25.0g (138mmol) were added to a 500 ml eggplant-shaped flask with a cooling tube. 35.9 g (260 mmol) of potassium carbonate and 200 ml of acetone were used as a mixture, and the reaction was carried out while stirring at 60 ° C for 48 hours. After the completion of the reaction, the solvent was distilled off under reduced pressure to give a yellow, dry solid. Thereafter, the solid was mixed with 200 ml of water, and 100 ml of chloroform was added thereto and extracted. The extraction was carried out 3 times.

The organic layer was separated, dried over anhydrous magnesium sulfate, and filtered, and the solvent was evaporated under reduced pressure to give a yellow solid. This solid was dissolved in chloroform, and precipitated with hexane (hexane/chloroform = 2/1) to afford 17.6 g of a white solid. The results of measurement of the solid by NMR are shown below. From the results, it was confirmed that the white solid was a compound (RM4-A) represented by the following reaction formula. The yield was 76%.

¹ H _- NMR (CDCl ₃ ) 6: 2.19 (m, 4H), 3.89 (m, 4H), 4.01 (m, 4H), 4.16 (m, 4H), 5.11 (m, 2H), 6.95 (m, 4H) ), 7.45 (m, 4H).

Next, 10.0 g (26 mmol) of the above-obtained compound (RM4-A), 10.0 g (60.6 mmol) of 2-(bromomethyl)acrylic acid, and 10% HCl (aq) were added to a 500 ml eggplant-shaped flask equipped with a cooling tube. 32 ml, 140 ml of tetrahydrofuran (THF), and 11.4 g (60.6 mmol) of tin (II) chloride were used as a mixture, and the mixture was stirred at 70 ° C for 20 hours to cause a reaction. After the completion of the reaction, the reaction mixture was filtered under reduced pressure, and then mixed with 200 ml of purified water, and then 100 ml of chloroform was added and extracted. The extraction was carried out 3 times.

Anhydrous magnesium sulfate was added to the organic layer after extraction to dryness, and the solvent was filtered off under reduced pressure to give a white solid. This solid was dissolved in chloroform and precipitated with hexane (hexane/chloroform = 2/1) to give a white solid. The solid was washed with methanol to give 4.7 g of a white solid. The results of measurement of the solid by NMR are shown below. From the results, it was confirmed that the white solid was a polymerizable compound (RM4) represented by the following reaction formula. The yield was 42%.

¹ H-NMR (CDCl ₃ ) δ: 2.18 (m, 4H), 2.76 (m, 2H), 3.16 (m, 2H), 4.18 (m, 4H), 4.84 (m, 2H), 5.67 (m, 2H) ), 6.27 (m, 2H), 6.95 (d, 4H), 7.46 (m, 4H).

<Modulation of liquid crystal alignment agent>

The abbreviations used in the preparation of the liquid crystal alignment agent described below are as follows.

BODA: bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride CBDA: 1,2,3,4-cyclobutane tetracarboxylic dianhydride

TCA: 2,3,5-tricarboxycyclopentyl acetic acid-1,4:2,3-dianhydride shown by the following formula

m-PDA: m-phenylene diamine

p-PDA: p-phenylenediamine

PCH: 1,3-diamino-4-[4-(4-heptylcyclohexyl)phenoxy]benzene

DBA: 3,5-diamino benzoic acid

DA-1: 2-(methacryloxy)ethyl 3,5-diaminobenzoate represented by the following formula

DA-2: N ¹ ,N ¹ -dipropyl phenyl-1,2,4-triamine represented by the following formula

DA-3: 3,5-diamino benzoic acid cholestyl ester shown by the following formula

3-AMP: 3-aminomethylpyridine

NMP: N-methyl-2-pyrrolidone

BCS: ethylene glycol dibutyl ether

Further, the molecular weight measurement conditions of the polyimine are as follows.

Device: room temperature gel permeation chromatography (GPC) device (SSC-7200) manufactured by Senshu Scientific Co., Ltd.

Column: Shodex pipe column (KD-803, KD-805)

Column temperature: 50 ° C

Dissolution: N,N'-dimethylformamide (as an additive, lithium bromide-hydrate (LiBr‧H ₂ O) is 30 mmol/L, phosphoric acid ‧ anhydrous crystal (o-phosphoric acid) is 30 mmol/L, tetrahydrofuran ( THF) is 10ml/L)

Flow rate: 1.0ml/min

Standard sample for calibration line preparation: TSK standard polyethylene oxide (molecular weight: about 900,000, 150,000, 100,000, 30,000) manufactured by Tosho Co., Ltd., and polyethylene glycol (molecular weight: about 12,000, 4,000, 1,000) manufactured by Polymer Laboratories Ltd. .

Further, the oxime imidization ratio of polyimine was measured as follows. 20 mg of polyimine powder was placed in an NMR sample tube (NMR standard sampling tube manufactured by Kusano Scientific Co., Ltd.), and 0.53 mL of deuterated dimethyl hydrazine (DMSO-d6, 0.05% TMS mixture) was added to make it in ultrasonic waves. It is completely dissolved. The proton NMR at 500 MHz of this solution was measured by an NMR measuring instrument (JNW-ECA500) manufactured by JEOL DATUM. The ruthenium imidization ratio is determined by a proton derived from a structure which does not change before and after the imidization, and the peak integral value of the proton and the NH group derived from proline which is present in the vicinity of 9.5 to 10.0 ppm are used. The proton peak integral value is obtained by the following equation. For the following formula, x represents the integral value of the proton peak derived from the NH group of proline, y represents the peak integral value of the reference proton, and α represents the proline acid when the polyproline (0% imidization ratio is 0%) The ratio of the number of reference protons corresponding to one NH matrix.

醯 imidization rate (%) = (1-α‧x/y) × 100

(Example 4)

BODA (28.15 g, 112.5 mmol), m-PDA (4.86 g, 45 mmol), PCH (11.42 g, 30 mmol), DBA (11.41 g, 75 mmol) were mixed in NMP (187.8 g), and carried out at 80 ° C for 5 hours. After the reaction, CBDA (6.77 g, 36 mmol) and NMP (62.6 g) were added, and the reaction was carried out at 40 ° C for 10 hours to obtain a polyaminic acid solution. After adding NMP to the polyamic acid solution (313 g) and diluting it to 6 mass%, acetic anhydride (79.1 g) and pyridine (30.7 g) were added as a ruthenium amide catalyst, and the reaction was carried out at 100 ° C for 3 hours. . The reaction solution was poured into methanol (4000 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (A). The polyimine had a hydrazine imidation ratio of 70%, a number average molecular weight of 18,000, and a weight average molecular weight of 59,000.

To the obtained polyimine powder (A) (6.0 g), NMP (40.2 g) was added, and the mixture was stirred at 50 ° C for 12 hours and dissolved. To this solution, 3-AMP 5.0 wt% NMP solution (6.0 g) (as 3-AMP 0.3 g), NMP (27.9 g), and BCS (20.0 g) were added, and the mixture was stirred at 50 ° C for 5 hours to obtain a liquid crystal alignment. Agent (A1).

In addition, 0.06 g (10% by mass of the solid content) of the polymerizable compound RM1 obtained in the above-mentioned liquid crystal alignment agent (A1) was stirred at room temperature for 3 hours to dissolve the liquid crystal. Orienting agent (A2). In the same manner, the polymerizable compound RM1 obtained in Example 1 was added to 0.10 g (30% by mass of the solid content) of the liquid crystal alignment agent (A1), and the mixture was stirred at room temperature for 3 hours to dissolve the liquid crystal. Orienting agent (A3).

(Example 5)

BODA (8.76 g, 35.0 mmol), p-PDA (3.78 g, 35.0 mmol), PCH (5.33 g, 14.0 mmol), DA-1 (5.55 g, 21.0 mmol) were mixed in NMP (90.0 g). After reacting at 80 ° C for 5 hours, CBDA (6.59 g, 33.6 mmol) and NMP (30.0 g) were added, and the reaction was carried out at 40 ° C for 10 hours to obtain a polyaminic acid solution. After the polyacrylic acid solution (140.0 g) was diluted with NMP to 6 mass%, acetic anhydride (20.0 g) and pyridine (25.8 g) were added as a ruthenium amide catalyst, and the reaction was carried out at 50 ° C for 3 hours. . The reaction solution was poured into methanol (1800 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (B). The polyamidimide had a ruthenium iodide ratio of 50%, a number average molecular weight of 22,000, and a weight average molecular weight of 77,000.

To the obtained polyimine powder (B) (6.0 g), NMP (74.0 g) was added, and the mixture was stirred at 50 ° C for 12 hours and dissolved. BCS (20.0 g) was added to the solution, and the mixture was stirred at 50 ° C for 5 hours to obtain a liquid crystal alignment agent (B1).

In addition, 0.06 g (10% by mass of the solid content) of the polymerizable compound RM1 obtained in Example 1 was added to 10.0 g of the liquid crystal alignment agent (B1), and the mixture was stirred and dissolved at room temperature for 3 hours to prepare a liquid crystal. Orienting agent (B2).

(Example 6)

BODA (3.13 g, 12.5 mmol), p-PDA (1.08 g, 10 mmol), PCH (1.90 g, 5 mmol), DA-1 (2.64 g, 10 mmol) were mixed in NMP (33.3 g) at 80 ° C After 5 hours of reaction, CBDA (2.35 g, 12 mmol) and NMP (11.1 g) were added, and the reaction was carried out at 40 ° C for 10 hours to obtain a polyaminic acid solution. After the polyacrylic acid solution (55.5 g) was diluted with NMP to 6 mass%, acetic anhydride (7.7 g) and pyridine (9.9 g) were added as a ruthenium amide catalyst, and the reaction was carried out at 50 ° C for 3 hours. . The reaction solution was poured into methanol (710 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (C). The polyimine had a ruthenium iodide ratio of 48%, a number average molecular weight of 26,000, and a weight average molecular weight of 102,000.

NMP (74.0 g) was added to the obtained polyimine powder (C) (6.0 g), and the mixture was stirred at 50 ° C for 12 hours and dissolved. BCS (20.0 g) was added to the solution, and the mixture was stirred at 50 ° C for 5 hours to obtain a liquid crystal alignment agent (C1).

In addition, 0.06 g (10% by mass of the solid content) of the polymerizable compound RM1 obtained in Example 1 was added to the above-mentioned liquid crystal alignment agent (C1), and the polymerizable compound RM1 obtained in Example 1 was stirred at room temperature for 3 hours to dissolve the liquid crystal. Orienting agent (C2).

(Example 7)

BODA (3.13 g, 12.5 mmol), p-PDA (0.81 g, 7.5 mmol), PCH (1.90 g, 5 mmol), DA-1 (3.30 g, 12.5 mmol) were mixed in NMP (34.5 g) at 80 After reacting for 5 hours at ° C, CBDA (2.35 g, 12 mmol) and NMP (11.5 g) were added, and the reaction was carried out at 40 ° C for 10 hours to obtain a polyaminic acid solution. After the polyacrylic acid solution (57.5 g) was diluted with NMP to 6 mass%, acetic anhydride (7.7 g) and pyridine (9.9 g) were added as a ruthenium amide catalyst, and the reaction was carried out at 50 ° C for 3 hours. . The reaction solution was poured into methanol (730 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (D). The polyimine had a hydrazide conversion ratio of 50%, a number average molecular weight of 23,000, and a weight average molecular weight of 63,000.

To the obtained polyimine powder (D) (6.0 g), NMP (74.0 g) was added, and the mixture was stirred at 50 ° C for 12 hours and dissolved. BCS (20.0 g) was added to the solution, and the mixture was stirred at 50 ° C for 5 hours to obtain a liquid crystal alignment agent (D1).

In addition, 0.06 g (10% by mass of solid content) of the polymerizable compound RM1 obtained in Example 1 was added to 10.0 g of the liquid crystal alignment agent (D1), and the mixture was stirred and dissolved at room temperature for 3 hours to prepare a liquid crystal. Orienting agent (D2).

(Example 8)

BODA (5.00 g, 20 mmol), p-PDA (0.87 g, 8 mmol), PCH (3.05 g, 8 mmol), DA-1 (6.34 g, 24 mmol) were mixed in NMP (57.1 g) at 80 ° C After an hour of reaction, CBDA (3.77 g, 19.2 mmol) and NMP (19.0 g) were added, and the reaction was carried out at 40 ° C for 10 hours to obtain a polyaminic acid solution. After the polyacrylic acid solution (95.5 g) was diluted with NMP to 6 mass%, acetic anhydride (12.3 g) and pyridine (15.9 g) were added as a ruthenium amide catalyst, and the reaction was carried out at 50 ° C for 3 hours. . The reaction solution was poured into methanol (1200 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (E). The polyamidimide had a ruthenium iodide ratio of 51%, a number average molecular weight of 31,000, and a weight average molecular weight of 111,000.

To the obtained polyimine powder (E) (6.0 g), NMP (74.0 g) was added, and the mixture was stirred at 50 ° C for 12 hours and dissolved. BCS (20.0 g) was added to the solution, and the mixture was stirred at 50 ° C for 5 hours to obtain a liquid crystal alignment agent (E1).

In addition, 0.06 g (10% by mass of solid content) of the polymerizable compound RM1 obtained in Example 1 was added to 10.0 g of the liquid crystal alignment agent (E1), and the mixture was stirred and dissolved at room temperature for 3 hours to prepare a liquid crystal. Orienting agent (E2).

(Example 9)

BODA (5.00 g, 20.0 mmol), p-PDA (2.16 g, 20.0 mmol), PCH (3.04 g, 8.0 mmol), DA-2 (2.44 g, 12.0 mmol) were mixed in NMP (49.2 g). After reacting at 80 ° C for 5 hours, CBDA (3.77 g, 19.2 mmol) and NMP (16.4 g) were added, and the reaction was carried out at 40 ° C for 10 hours to obtain a polyaminic acid solution. After the polyacrylic acid solution (75.0 g) was diluted with NMP to 6 mass%, acetic anhydride (9.33 g) and pyridine (14.6 g) were added as a ruthenium amide catalyst, and the reaction was carried out at 50 ° C for 3 hours. . The reaction solution was poured into methanol (950 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (F). The polyamidimide had a ruthenium iodide ratio of 47%, a number average molecular weight of 20,100, and a weight average molecular weight of 106,000.

To the obtained polyimine powder (F) (6.0 g), NMP (74.0 g) was added, and the mixture was stirred at 50 ° C for 12 hours and dissolved. BCS (20.0 g) was added to the solution, and the mixture was stirred at 50 ° C for 5 hours to obtain a liquid crystal alignment agent (F1).

In addition, 0.06 g (10% by mass of the solid content) of the polymerizable compound RM1 obtained in Example 1 was added to 10.0 g of the liquid crystal alignment agent (F1), and the mixture was stirred and dissolved at room temperature for 3 hours to prepare a liquid crystal. Orienting agent (F2).

(Embodiment 10)

BODA (5.00 g, 20.0 mmol), p-PDA (0.87 g, 8.0 mmol), PCH (3.04 g, 8.0 mmol), DA-2 (4.88 g, 24.0 mmol) were mixed in NMP (52.7 g). After reacting at 80 ° C for 5 hours, CBDA (3.77 g, 19.2 mmol) and NMP (17.56 g) were added, and the reaction was carried out at 40 ° C for 10 hours to obtain a polyaminic acid solution. After adding NMP to the polyamic acid solution (75 g) and diluting it to 6 mass%, acetic anhydride (8.7 g) and pyridine (13.5 g) were added as a ruthenium amide catalyst, and the reaction was carried out at 50 ° C for 3 hours. The reaction solution was poured into methanol (950 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (G). The polyimine has a hydrazine imidation ratio of 50%, a number average molecular weight of 20,000, and a weight average molecular weight of 86,000.

To the obtained polyimine powder (G) (6.0 g), NMP (74.0 g) was added, and the mixture was stirred at 50 ° C for 12 hours and dissolved. BCS (20.0 g) was added to the solution, and the mixture was stirred at 50 ° C for 5 hours to obtain a liquid crystal alignment agent (G1).

In addition, 0.06 g (10% by mass of the solid content) of the polymerizable compound RM1 obtained in Example 1 was added to 10.0 g of the liquid crystal alignment agent (G1), and the mixture was stirred and dissolved at room temperature for 3 hours to prepare a liquid crystal. Orienting agent (G2).

(Example 11)

TCA (3.36 g, 15.0 mmol), p-PDA (1.30 g, 12.0 mmol), DA-3 (3.14 g, 6.0 mmol), DA-1 (3.17 g, 12.0 mmol) were mixed in NMP (41.6 g). After reacting at 60 ° C for 5 hours, CBDA (2.88 g, 14.7 mmol) and NMP (13.9 g) were added, and the reaction was carried out at 40 ° C for 10 hours to obtain a polyaminic acid solution. After adding NMP to the polyamic acid solution (68 g) and diluting it to 6 mass%, acetic anhydride (6.0 g) and pyridine (11.7 g) were added as a ruthenium amide catalyst, and the reaction was carried out at 50 ° C for 3 hours. . The reaction solution was poured into methanol (850 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (H). The polyamidimide had a ruthenium iodide ratio of 50%, a number average molecular weight of 18,000, and a weight average molecular weight of 58,000.

To the obtained polyimine powder (H) (6.0 g), NMP (74.0 g) was added, and the mixture was stirred at 50 ° C for 12 hours and dissolved. BCS (20.0 g) was added to the solution, and the mixture was stirred at 50 ° C for 5 hours to obtain a liquid crystal alignment agent (H1).

In addition, 0.06 g (10 wt% of the solid content) of RM1 was added to 10.0 g of the liquid crystal alignment agent (H1), and the mixture was stirred and dissolved at room temperature for 3 hours to prepare a liquid crystal alignment agent (H2).

(Embodiment 12)

BODA (6.01 g, 24.0 mmol), p-PDA (2.60 g, 24.0 mmol), PCH (6.85 g, 18.0 mmol), DA-1 (4.76 g, 18.0 mmol) were dissolved in NMP (81.5 g). After reacting at 80 ° C for 5 hours, CBDA (6.94 g, 35.4 mmol) and NMP (27.2 g) were added, and the reaction was carried out at 40 ° C for 10 hours to obtain a polyaminic acid solution. After adding NMP to the polyamic acid solution (135 g) and diluting it to 6 mass%, acetic anhydride (18.3 g) and pyridine (23.6 g) were added as a ruthenium catalyzed catalyst, and the reaction was carried out at 50 ° C for 3 hours. . Will reverse The solution was poured into methanol (1700 ml), and the resulting precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (I). The polyimine has a hydrazide conversion ratio of 60%, a number average molecular weight of 12,000, and a weight average molecular weight of 39,000.

To the obtained polyimine powder (I) (6.0 g), NMP (74.0 g) was added, and the mixture was stirred at 50 ° C for 12 hours and dissolved. BCS (20.0 g) was added to the solution, and the mixture was stirred at 50 ° C for 5 hours to obtain a liquid crystal alignment agent (I1).

0.06 g of the polymerizable compound (RM4) obtained above (10% by mass for the solid content) was added to 10.0 g of the liquid crystal alignment agent (I1), and the mixture was stirred and dissolved at room temperature for 3 hours to prepare a liquid crystal alignment agent (I2). ).

<Modulation of liquid crystal containing a polymerizable compound>

The liquid crystal containing a polymerizable compound was prepared as follows. To 20 g of MLC-6608 (trade name, manufactured by Mock Corporation), 0.0147 g (3 × 10 ^-5 mol) of the polymerizable compound RM1 obtained in Example 1 was added, and the mixture was stirred and dissolved at 80 ° C for 3 hours to prepare a solution. Liquid crystal 1.

In the same manner, 0.0097 g (3 × 10 ^-5 mol) of the polymerizable compound RM2 obtained in Example 2 was added to 20 g of MLC-6608, and the mixture was stirred and dissolved at 80 ° C for 3 hours to prepare a liquid crystal 2 .

Further, 0.0097 g (3 × 10 ^-5 mol) of the polymerizable compound RM3 obtained in Comparative Example 1 was added to 20 g of MLC-6608, and the mixture was stirred and dissolved at 80 ° C for 3 hours to prepare a liquid crystal 3 .

In addition, in the liquid crystal material MLC-6608, the liquid crystal 1, the liquid crystal 2, and the liquid crystal 3 were each dissolved in the liquid crystal material MLC-6608, and it was confirmed that the polymerizable compound was not precipitated after being stored for one month.

<Production of liquid crystal cells> (Example 13)

Using the liquid crystal alignment agent (A1) obtained in Example 4, the production of liquid crystal cells was carried out in the order shown below. The liquid crystal alignment agent (A1) obtained in Example 4 was spin-coated on an ITO surface of an ITO electrode substrate having an ITO electrode pattern having a pixel size of 100 μm × 300 μm and a line/pitch of 5 μm, and a heating plate at 80 ° C. After drying for 90 seconds, it was baked in a hot air circulating oven at 200 ° C for 30 minutes to form a liquid crystal alignment film having a thickness of 100 nm.

Further, the liquid crystal alignment agent (A1) was spin-coated on the ITO surface on which the electrode pattern was not formed, and dried on a hot plate at 80 ° C for 90 seconds, and then baked in a hot air circulating oven at 200 ° C for 30 minutes. A liquid crystal alignment film having a film thickness of 100 nm was formed.

On the two substrates, a 6 μm bead spacer was spread on the liquid crystal alignment film of one of the substrates, and then a sealant (solvent-type thermosetting epoxy resin) was applied from the upper surface. Next, the surface of the liquid crystal alignment film forming the other substrate was set to the inside, and after bonding to the previous substrate, the sealant was cured to prepare a hollow cell. The liquid crystal 1 was injected into the cell by a reduced pressure injection method, and Isotropic treatment (re-alignment treatment by heated liquid crystal) was performed in an oven at 120 ° C to prepare a liquid crystal cell.

The post-production response speed of the obtained liquid crystal cell was measured by the following method. Thereafter, in a state where a voltage of 20 Vp-p was applied to the liquid crystal cell, UV5J passing through a 313 nm band-pass filter was irradiated from the outside of the liquid crystal cell. Thereafter, the response speed was measured again, and the response speed before and after the UV irradiation was compared. The results of the response speeds of the liquid crystal cells after the preparation (initial) and after the irradiation of UV (after UV irradiation) are shown in Table 2.

"Method for measuring response speed"

First, a set of a measuring device including a polarizing plate and a light amount detector in a state of a backlight and a quadrature polarization state is disposed, and liquid crystal cells are disposed between a group of polarizing plates. At this time, the pattern of the ITO electrode formed by the line/pitch is made to be an angle of 45° for the orthogonal polarized light. In the above-mentioned liquid crystal cell, a rectangular wave with a voltage of ±4 V and a frequency of 1 kHz is applied, and the change in brightness observed by the light amount detector is read by an oscilloscope, and the brightness when the voltage is not applied is 0%, plus ± The voltage of 4V, and the value of the saturation brightness is taken as 100%, and the time when the brightness is changed from 10% to 90% is taken as the response speed.

(Example 14)

The same operation as in Example 13 was carried out, except that the liquid crystal 2 was used instead of the liquid crystal 1, and the response speed before and after the UV irradiation was compared.

(Comparative Example 2)

The same operation as in Example 13 was carried out, except that the liquid crystal 3 was used instead of the liquid crystal 1, and the response speed before and after the UV irradiation was compared.

(Example 15)

A liquid crystal alignment agent (A2) was used instead of the liquid crystal alignment agent (A1), and MLC-6608 was used instead of the liquid crystal 1, and the same operation as in Example 13 was carried out except that the UV substitution 5J irradiation was performed using 20 J, and the response before and after the UV irradiation was compared. speed.

(Embodiment 16)

The reaction speed before and after UV irradiation was compared in the same manner as in Example 15 except that the liquid crystal alignment agent (A2) was used instead of the liquid crystal alignment agent (A2).

(Comparative Example 3)

The reaction speed before and after UV irradiation was compared in the same manner as in Example 15 except that the liquid crystal alignment agent (A2) was used instead of the liquid crystal alignment agent (A2).

(Example 17)

The reaction speed before and after UV irradiation was compared in the same manner as in Example 15 except that the liquid crystal alignment agent (A2) was used instead of the liquid crystal alignment agent (B2).

(Comparative Example 4)

The reaction speed before and after UV irradiation was compared in the same manner as in Example 15 except that the liquid crystal alignment agent (A2) was used instead of the liquid crystal alignment agent (B2).

(Embodiment 18)

The reaction speed before and after UV irradiation was compared in the same manner as in Example 15 except that the liquid crystal alignment agent (A2) was used instead of the liquid crystal alignment agent (C2).

(Comparative Example 5)

The reaction speed before and after UV irradiation was compared in the same manner as in Example 15 except that the liquid crystal alignment agent (A2) was used instead of the liquid crystal alignment agent (C2).

(Embodiment 19)

The reaction speed before and after UV irradiation was compared in the same manner as in Example 15 except that the liquid crystal alignment agent (A2) was used instead of the liquid crystal alignment agent (D2).

(Comparative Example 6)

The reaction speed before and after the UV irradiation was compared in the same manner as in Example 15 except that the liquid crystal alignment agent (A2) was used instead of the liquid crystal alignment agent (A2).

(Embodiment 20)

The reaction speed before and after UV irradiation was compared in the same manner as in Example 15 except that the liquid crystal alignment agent (A2) was used instead of the liquid crystal alignment agent (A2).

(Comparative Example 7)

The reaction speed before and after UV irradiation was compared in the same manner as in Example 15 except that the liquid crystal alignment agent (A2) was used instead of the liquid crystal alignment agent (A2).

(Example 21)

The reaction speed before and after UV irradiation was compared in the same manner as in Example 15 except that the liquid crystal alignment agent (A2) was used instead of the liquid crystal alignment agent (F2).

(Comparative Example 8)

The reaction speed before and after UV irradiation was compared in the same manner as in Example 15 except that the liquid crystal alignment agent (A2) was used instead of the liquid crystal alignment agent (F2).

(Example 22)

The reaction speed before and after UV irradiation was compared in the same manner as in Example 15 except that the liquid crystal alignment agent (A2) was used instead of the liquid crystal alignment agent (A2).

(Comparative Example 9)

The reaction speed before and after UV irradiation was compared in the same manner as in Example 15 except that the liquid crystal alignment agent (A2) was used instead of the liquid crystal alignment agent (A2).

(Example 23)

The reaction speed before and after UV irradiation was compared in the same manner as in Example 15 except that the liquid crystal alignment agent (A2) was used instead of the liquid crystal alignment agent (H2).

As a result, as shown in Table 2, the rate of improvement of the response speed after ultraviolet irradiation of the response speeds of ultraviolet rays before irradiation of Examples 13 and 14 in which the polymerizable compound represented by the above formula (1) is contained in the liquid crystal is contained in the past. Comparative Example 2 of the polymerizable compound was significantly improved. Therefore, since the liquid crystal contains the polymerizable compound represented by the above formula (1), even if the amount of the polymerizable compound added to the liquid crystal is small, it is confirmed that the response speed can be greatly improved.

Further, in the above formula (1), Example 13 using a polymerizable compound in which V and W are an oxyalkylene group is used, and Example 14 in which a polymerizable compound having a single bond of V and W is used as the above formula (1), The rate of increase in response speed is significantly higher.

In addition, in the liquid crystal alignment agent, the upward rate of the response speed before and after the ultraviolet irradiation of Examples 15 to 23 of the polymerizable compound represented by the above formula (1) is not included in the liquid crystal alignment agent, and the polymerizable property represented by the above formula (1) is not contained. Comparative Examples 3 to 9 of the compounds were significantly higher. Therefore, it has been confirmed that the liquid crystal alignment agent contains the polymerizable compound represented by the above formula (1), and the response speed can be greatly improved. Further, it was confirmed that the rate of improvement of the response speed was higher as compared with the comparative examples corresponding to the examples 15 to 23 in which the polyimine type was changed.

Further, in Example 16 in which the amount of the polymerizable compound added in the above formula (1) was 30% by mass, the rate of improvement in the response rate was higher than that in Example 15 in which the amount of addition was 10% by mass. Therefore, it is confirmed that the larger the amount of the polymerizable compound represented by the above formula (1), the higher the response speed.

Further, Examples 17 to 23 using a photoreactive group of polyimine showed a remarkable increase in response speed than Example 15 using a polyimide having no photoreactive group, and it was confirmed that photoreactivity was used. When the polyimine is based, the response speed can be further increased.

(Example 24)

To the 10.0 g of the liquid crystal alignment agent (D1), 0.06 g (10% by mass of the solid content) of the polymerizable compound RM2 obtained in Example 2 was stirred at room temperature for 3 hours and dissolved to prepare a liquid crystal alignment agent. (D3).

(Comparative Example 10)

The polymerizable compound RM3 of Comparative Example 1 in which 0.06 g (10% by mass of the solid content) was added to 10.0 g of the liquid crystal alignment agent (D1) was stirred and dissolved at room temperature for 3 hours to prepare a liquid crystal alignment agent ( D4).

(Embodiment 25)

The reaction speed before and after UV irradiation was compared in the same manner as in Example 19, except that the liquid crystal alignment agent (D2) was used instead of the liquid crystal alignment agent (D2). The results are shown in Table 3.

(Example 26)

The same operation as in Example 25 was carried out except that the firing of the thermocycling oven at 200 ° C for 30 minutes was changed to 160 ° C for 30 minutes, and the response speed before and after the UV irradiation was compared.

(Comparative Example 11)

The reaction speed before and after UV irradiation was compared in the same manner as in Example 25 except that the liquid crystal alignment agent (D3) was used instead of the liquid crystal alignment agent (D3).

(Comparative Example 12)

The same operation as in Comparative Example 11 was carried out except that the firing at 200 ° C for 30 minutes in a heat cycle oven was changed to 30 minutes at 160 ° C, and the response speed before and after UV irradiation was compared.

(Example 27)

The reaction speed before and after the UV irradiation was compared in the same manner as in Example 15 except that the liquid crystal alignment agent (A2) was used instead of the liquid crystal alignment agent (A2).

(Embodiment 28)

The firing rate was changed from 200 ° C to 140 ° C, and the same operation as in Example 27 was carried out to compare the response speed before and after UV irradiation.

(Comparative Example 13)

The reaction speed before and after the UV irradiation was compared in the same manner as in Example 27 except that the liquid crystal alignment agent (I2) was used instead of the liquid crystal alignment agent (I2).

(Comparative Example 14)

The firing rate was changed from 200 ° C to 140 ° C, and the same operation as in Comparative Example 13 was carried out, and the response speed before and after UV irradiation was compared.

As a result, in Examples 25 to 28 in which the liquid crystal alignment agent containing the polymerizable compound represented by the above formula (1) was used, the response speed was sufficiently improved by UV irradiation regardless of the firing temperature. On the other hand, in Comparative Example in which a liquid crystal alignment agent containing RM3 of a conventional polymerizable compound was used, in Comparative Example 11 in which the firing temperature was 160 ° C, a sufficient response speed was observed by UV irradiation, but the firing temperature was increased. In Comparative Example 12 at 200 ° C, the rate of increase in response speed was remarkably lowered. Further, in Comparative Example 13 and Comparative Example 14 in which a liquid crystal alignment agent to which a polymerizable compound was not added, the response speed before and after the ultraviolet irradiation was hardly changed at all the firing temperatures.

The abbreviations used below are as follows.

TEOS: tetraethoxy decane

C18: octadecyltriethoxydecane

ACPS: 3-propoxypropyltrimethoxydecane

UPS: 3-guanidinopropyl triethoxy decane

MPMS: 3-methacryloxypropyltrimethoxydecane

VTES: triethoxyethylene decane

NMP: N-methyl-2-pyrrolidone

HG: 2-methyl-2,4-pentanediol (alias: hexanediol)

BCS: 2-butoxyethanol

<Production of liquid crystal alignment agent of polyoxyalkylene system> (Comparative Example 15)

A solution of 24.5 g of BCS, 32.4 g of TEOS, and 1.34 g of C18 was mixed in a 100 mL four-neck reaction flask equipped with a thermometer and a reflux tube to prepare a solution of an alkoxydecane monomer. A solution of 12.3 g of BCS, 8.65 g of water, and 0.14 g of oxalic acid as a catalyst was preliminarily mixed in the solution, and the mixture was added dropwise at room temperature for 30 minutes. After the solution was stirred for 30 minutes and refluxed for 30 minutes, a mixed liquid of 0.46 g of a methanol solution having a UPS content of 92% by mass and 0.34 g of BCS was added. Further, the mixture was refluxed for 30 minutes, and then cooled to obtain a polyoxane solution having a SiO ₂ conversion concentration of 12% by mass.

38.0 g of the obtained polyoxane solution, 3.63 g of BCS, and 49.6 g of NMP were mixed to obtain a liquid crystal alignment agent (a) having a SiO ₂ conversion concentration of 5% by mass.

(Example 29)

The liquid crystal alignment agent (a) obtained in Comparative Example 15 was added with a polymerizable compound RM1 to 10% by mass, and stirred at room temperature for 5 hours to prepare a varnish (liquid crystal alignment agent).

(Embodiment 30)

The liquid crystal alignment agent (a) obtained in Comparative Example 15 was added with a polymerizable compound RM1 to 20% by mass, and stirred at room temperature for 5 hours to prepare a varnish (liquid crystal alignment agent).

(Example 31)

The liquid crystal alignment agent (a) obtained in Comparative Example 15 was added to the polymerizable compound RM 2 to 10% by mass, and stirred at room temperature for 5 hours to prepare a varnish (liquid crystal alignment agent).

(Comparative Example 16)

In a four-neck reaction flask equipped with a thermometer and a reflux tube, 24.5 g of BCS, 25.7 g of TEOS, C18 of 1.33 g, and 6.09 g of VTES were mixed to prepare a solution of an alkoxydecane monomer. To the solution, a premixed solution of 12.3 g of BCS, 8.64 g of water, and 0.72 g of oxalic acid as a catalyst was added dropwise at room temperature for 30 minutes. After the solution was stirred for 30 minutes and refluxed for 30 minutes, a mixed liquid of 0.46 g of a methanol solution having a UPS content of 92% by mass and 0.34 g of BCS was added. Further, the mixture was refluxed for 30 minutes, and then cooled to obtain a polyoxane solution having a SiO ₂ conversion concentration of 12% by mass.

38.0 g of the obtained polyoxane solution, 3.63 g of BCS, and 49.6 g of NMP were mixed to obtain a liquid crystal alignment agent (b) having a SiO ₂ conversion concentration of 5% by mass.

(Example 32)

The polymerizable compound RM1 to 10% by mass was added to the liquid crystal alignment agent (b) obtained in Comparative Example 16, and the mixture was stirred at room temperature for 5 hours to prepare a varnish (liquid crystal alignment agent).

(Example 33)

The polymerizable compound RM 2 to 10% by mass was added to the liquid crystal alignment agent (b) obtained in Comparative Example 16, and the mixture was stirred at room temperature for 5 hours to prepare a varnish (liquid crystal alignment agent).

(Comparative Example 17)

In a four-neck reaction flask equipped with a thermometer and a reflux tube, BCS 23.3 g, TEOS 22.3 g, 1.33 g of C18, and ACPS 11.3 g were mixed to prepare a solution of an alkoxydecane monomer. To the solution, 11.6 g of BCS, 8.64 g of water, and 0.72 g of oxalic acid as a catalyst were mixed and mixed at room temperature for 30 minutes. This solution was stirred for 30 minutes, and after refluxing for 30 minutes, a mixed liquid of 0.46 g of a methanol solution having a UPS content of 92% by mass and 0.34 g of BCS was added. Further, the mixture was refluxed for 30 minutes, and then cooled to obtain a polyoxane solution having a SiO ₂ conversion concentration of 12% by mass.

38.0 g of the obtained polyoxane solution, 4.24 g of BCS, and 49.0 g of NMP were mixed to obtain a liquid crystal alignment agent (c) having a SiO ₂ conversion concentration of 5% by mass.

(Example 34)

The polymerizable compound RM1 to 5 mass% was added to the liquid crystal alignment agent (c) obtained in Comparative Example 17, and the mixture was stirred at room temperature for 5 hours to prepare a varnish (liquid crystal alignment agent).

(Example 35)

The polymerizable compound RM1 to 10% by mass was added to the liquid crystal alignment agent (c) obtained in Comparative Example 17, and the mixture was stirred at room temperature for 5 hours to prepare a varnish (liquid crystal alignment agent).

(Comparative Example 18)

Into the liquid crystal alignment agent (c) obtained in Comparative Example 17, 3 to 10% by mass of the polymerizable compound RM was added, and the mixture was stirred at room temperature for 5 hours to prepare a varnish (liquid crystal alignment agent).

(Comparative Example 19)

In a four-neck reaction flask equipped with a thermometer and a reflux tube, BCS 23.4 g, TEOS 25.7 g, 1.33 g of C18, and MPMS 7.95 g were mixed to prepare a solution of an alkoxydecane monomer. To the solution, a premixed solution of 11.7 g of BCS, 8.64 g of water, and 0.58 g of oxalic acid as a catalyst was added dropwise at room temperature for 30 minutes. This solution was stirred for 30 minutes, and after refluxing for 30 minutes, a mixed liquid of 0.46 g of a methanol solution having a UPS content of 92% by mass and 0.34 g of BCS was added. Further, the mixture was refluxed for 30 minutes, and then cooled to obtain a polyoxane solution having a SiO ₂ conversion concentration of 12% by mass.

38.0 g of the obtained polyoxane solution, 4.20 g of BCS, and 49.0 g of NMP were mixed to obtain a liquid crystal alignment agent (d) having a SiO ₂ conversion concentration of 5% by mass.

(Example 36)

The polymerizable compound RM1 to 5 mass% was added to the liquid crystal alignment agent (d) obtained in Comparative Example 19, and the mixture was stirred at room temperature for 5 hours to prepare a varnish (liquid crystal alignment agent).

(Example 37)

The polymerizable compound RM1 to 10% by mass was added to the liquid crystal alignment agent (d) obtained in Comparative Example 19, and the mixture was stirred at room temperature for 5 hours to prepare a varnish (liquid crystal alignment agent).

(Comparative Example 20)

Into the liquid crystal alignment agent (d) obtained in Comparative Example 19, 3 to 10% by mass of the polymerizable compound RM was added, and the mixture was stirred at room temperature for 5 hours to prepare a varnish (liquid crystal alignment agent).

<Production of liquid crystal cells> (Example 38)

Using the varnish (liquid crystal alignment agent) obtained in Example 29, the production of liquid crystal cells was carried out in the order shown below. First, the varnish obtained in Example 29 was spin-coated on an ITO surface of an ITO electrode substrate having an ITO electrode pattern having a pixel size of 100 μm × 300 μm and a line/pitch of 5 μm, and was baked on a hot plate at 80 ° C for 5 minutes. After drying, it was baked in a hot air circulating oven at 200 ° C for 30 minutes to form a liquid crystal alignment film having a film thickness of 100 nm.

Further, the liquid crystal alignment agent (a) obtained in Comparative Example 15 was spin-coated on an ITO surface on which no electrode pattern was formed, and dried on a hot plate at 80 ° C for 5 minutes, and then in a hot air circulating oven at 200 ° C. The film was fired for 30 minutes to form a liquid crystal alignment film having a film thickness of 100 nm.

On the two substrates, a 6 μm bead spacer was spread on the liquid crystal alignment film of one of the substrates, and then a sealant (solvent-type thermosetting epoxy resin) was applied from the upper surface. Next, the surface of the liquid crystal alignment film forming the other substrate was set to the inside, and after bonding to the previous substrate, the sealant was cured to prepare a hollow cell. In this empty cell, liquid crystal MLC-6608 (trade name of Mock Corporation) was injected by a reduced pressure injection method, and isotropic treatment was carried out in an oven at 120 ° C (recrystallization treatment by heating to form a liquid crystal cell). .

The post-production response speed of the obtained liquid crystal cell was measured by the following method. Thereafter, in a state where a voltage of 20 Vp-p was applied to the liquid crystal cell, UV10J passing through a 313 nm band-pass filter was irradiated from the outside of the liquid crystal cell. Thereafter, the response speed was measured again, and the response speed before and after the UV irradiation was compared. The results of the response speeds of the liquid crystal cells after the preparation (initial), after UV5J irradiation (after UV5J), and after irradiation of UV10J (after UV10J) are shown in Table 4.

"Method for measuring response speed"

First, a set of a measuring device including a polarizing plate and a light amount detector in a state of a backlight and a quadrature polarization state is disposed, and liquid crystal cells are disposed between a group of polarizing plates. At this time, the pattern of the ITO electrode formed by the line/pitch is made to be an angle of 45° for the orthogonal polarized light. In the above-mentioned liquid crystal cell, a rectangular wave with a voltage of ±4 V and a frequency of 1 kHz is applied, and the change in brightness observed by the light amount detector is read by an oscilloscope, and the brightness when the voltage is not applied is 0%, plus ± The voltage of 4V, and the value of the saturation brightness is taken as 100%, and the time when the brightness is changed from 10% to 90% is taken as the response speed.

(Example 39)

The same procedure as in Example 38 was carried out, except that the varnish obtained in Example 29 was used, except that the varnish obtained in Example 30 was used.

(Embodiment 40)

The same procedure as in Example 38 was carried out, except that the varnish obtained in Example 29 was used, except that the varnish obtained in Example 31 was used.

(Example 41)

The same procedure as in Example 38 was carried out, except that the varnish obtained in Example 29 was used, except that the varnish obtained in Example 32 was used.

(Example 42)

The same procedure as in Example 38 was carried out, except that the varnish obtained in Example 29 was used, except that the varnish obtained in Example 33 was used.

(Example 43)

The same procedure as in Example 38 was carried out, except that the varnish obtained in Example 29 was used, and the varnish obtained in Example 34 was irradiated with UV-substituted 10J at 5 J.

(Example 44)

The same procedure as in Example 38 was carried out, except that the varnish obtained in Example 29 was used, and the varnish obtained in Example 35 was irradiated with UV-substituted 10J at 5 J.

(Example 45)

The same procedure as in Example 38 was carried out, except that the varnish obtained in Example 29 was used, and the varnish obtained in Example 36 was irradiated with UV-substituted 10J at 5 J.

(Example 46)

The same procedure as in Example 38 was carried out, except that the varnish obtained in Example 29 was used, and the varnish obtained in Example 37 was irradiated with UV-substituted 10J at 5 J.

(Comparative Example 21)

The same procedure as in Example 38 was carried out, except that the varnish obtained in Example 29 was used, except for the liquid crystal alignment agent (a) obtained in Comparative Example 15.

(Comparative Example 22)

The same procedure as in Example 38 was carried out, except that the varnish obtained in Example 29 was used, except that the liquid crystal alignment agent (b) obtained in Comparative Example 16 was used.

(Comparative Example 23)

The same procedure as in Example 38 was carried out, except that the varnish obtained in Example 29 was used, and the liquid crystal alignment agent (c) obtained in Comparative Example 17 was used, and the UV substitution 10J irradiation was carried out using 5J irradiation.

(Comparative Example 24)

The same procedure as in Example 38 was carried out, except that the varnish obtained in Example 29 was used, and the varnish obtained in Comparative Example 18 was irradiated with UV-substituted 10J at 5 J.

(Comparative Example 25)

The liquid crystal alignment agent (d) obtained in Comparative Example 19 was used instead of the varnish obtained in Example 29, and the same operation as in Example 38 was carried out except that the UV substitution 10J irradiation was performed using 5J irradiation.

(Comparative Example 26)

The same procedure as in Example 38 was carried out, except that the varnish obtained in Example 29 was used, and the varnish obtained in Comparative Example 20 was irradiated with UV-substituted 10J at 5 J.

As shown in Table 4, in Examples 38 to 46 in which the liquid crystal alignment agent containing the polymerizable compound represented by the above formula (1) was used, the rate of improvement of the response speed before and after the ultraviolet irradiation was used, and the alignment of the liquid crystal containing no polymerizable compound was used. In Comparative Examples 21 to 23 and 25, or Comparative Examples 24 and 26 using a liquid crystal alignment agent containing a polymerizable compound not containing the polymerizable compound represented by the above formula (1), it was remarkably high. Therefore, when the liquid crystal alignment agent contains the polymerizable compound represented by the above formula (1), it is confirmed that the response speed can be greatly improved. On the other hand, in comparison with the comparative examples corresponding to any of Examples 38 to 46 in which the polyoxyalkylene species were changed, it was confirmed that the rate of improvement in the response speed was high.

In addition, it was confirmed that the larger the amount of the polymerizable compound represented by the above formula (1), the higher the response speed.

Further, Examples 41 to 46 using a photoreactive group of polyoxyalkylene showed higher remarkable response speeds than Examples 38 to 40 using a polyoxyalkylene having no photoreactive group, and a photoreaction was used. In the case of a polyoxyalkylene group, it was confirmed that the response speed was further improved.

When the liquid crystal alignment agent of the present invention containing the polymerizable compound represented by the above formula (1) is used, the reaction rate can be accelerated even if the liquid crystal does not contain a polymerizable compound. In the liquid crystal alignment agent of the present invention, even if a large amount of the polymerizable compound is not added, the response speed can be sufficiently accelerated even if the amount of ultraviolet light irradiation is not large.

[Industrial availability]

By using the liquid crystal display element produced by the liquid crystal alignment agent of the present invention, the alignment method to the PSA method can be improved, and even when a liquid crystal to which a polymerizable compound is not added is used, a liquid crystal display element having the same characteristics as the PSA method can be obtained. As a result, it is useful for a PSA type TFT (Thin Film Transistor) liquid crystal display element, a TN (Twisted Nematic) liquid crystal display element, a VA liquid crystal display element, or the like.

Claims (10)

A liquid crystal alignment agent characterized by having a polymerizable compound represented by the following formula (1), a polymer forming a liquid crystal alignment film which is perpendicular to a liquid crystal alignment, and a solvent; (In the formula (1), V represents a single bond or -R ¹ O-, R ¹ is a linear or branched alkyl group having 1 to 10 carbon atoms, and W represents a single bond or -OR ² -, and R ² is straight The chain or branch has a carbon number of 1 to 10 alkyl groups). The liquid crystal alignment agent of claim 1, wherein the polymer forming the liquid crystal alignment film which is perpendicular to the liquid crystal comprises a polyimine precursor selected from the group consisting of a side chain having a liquid crystal alignment direction, and The polyimine precursor is subjected to at least one of the polyimine obtained by quinone imidization. The liquid crystal alignment agent of claim 1, wherein the polymer which forms the liquid crystal alignment film which is perpendicular to the liquid crystal is a polyoxyalkylene having a side chain which is perpendicular to the liquid crystal alignment. The liquid crystal alignment agent of claim 3, wherein the polyoxyalkylene is a photoreactive side chain. The liquid crystal alignment agent of claim 3, wherein the polyoxyalkylene is obtained by polycondensing at least one selected from the group consisting of alkoxysilane and the condensate. The liquid crystal alignment agent of claim 5, wherein the alkoxydecane is an alkoxydecane represented by the following formula (7); R ¹¹ Si(OR ¹² ) ₃ (7) (R ¹¹ represents A hydrocarbon group having 8 to 30 carbon atoms in the hydrogen atom may be replaced by a fluorine atom, and R ¹² represents an alkyl group having 1 to 5 carbon atoms. The liquid crystal alignment agent of claim 5 or 6, wherein the alkoxydecane is a compound of the following formula (8); R ¹³ Si(OR ¹⁴ ) ₃ (8) (R ¹³ represents a group selected from a propenyl group) And an alkyl group in which at least one of a methacryl group, a vinyl group, an epoxy group, a vinyloxy group, and a propylene group is substituted with hydrogen, and R ¹⁴ represents an alkyl group having 1 to 5 carbon atoms. A liquid crystal alignment film which is obtained by applying a liquid crystal alignment agent according to any one of claims 1 to 7 to a substrate and firing the resultant. A liquid crystal display element comprising the liquid crystal alignment film of item 8 of the patent application. A method for producing a liquid crystal display device, characterized in that a liquid crystal layer composed of a liquid crystal is held by a liquid crystal alignment film formed by a liquid crystal alignment agent according to any one of claims 1 to 7 A liquid crystal cell is produced by applying a voltage to the sheet substrate while irradiating ultraviolet rays.